In Setting the World on Its Buneary!, Buneary was close by when Ash's Pikachu was almost run over by Officer Jenny while trying to get back Ash's hat from his Aipom. It managed to rescue Pikachu and stayed near the group's campsite after that, but Brock's Croagunk noticed it was hiding in the bushes and it ran off. Both Ash and Dawn rushed to catch Buneary, but Dawn was determined to battle the Pokémon after failing to catch a Buneary in her previous attempts to do so. She quickly commanded Piplup to use Bubble Beam. However, Buneary was able to dodge Piplup's moves and confuse him with Dizzy Punch before using Bounce to knock him out.
After that, it was Ash's turn to try to catch Buneary. He used his Pikachu to battle Buneary, but it acted completely different than when battling Piplup before, covering its face with its fur. It then froze Ash, Dawn, and Brock with Ice Beam and started dancing with Pikachu. Pikachu later scolded Buneary for its actions, upsetting it and making it cry. Buneary stopped crying when it heard something. However, this did not prevent it from being locked inside a glass ball from Team Rocket's newest mecha. Pikachu offered to go with Jessie, James, and Meowth if they agreed to free Buneary, but the trio had no plans of letting Buneary go and just wanted to capture Pikachu for their boss. Using Iron Tail, Pikachu managed to break free and save Buneary. Together, they were able to wreck Team Rocket's mecha and then jump before it could explode, with Ash grabbing Pikachu and Buneary landing safely on Dawn's arms. Buneary was later asked if it would like to travel with Dawn. It agreed, but Dawn said they still should have a Pokémon battle.
This time, Piplup was prepared for Buneary's moves. Their battle began with Piplup using Bubble Beam, which Buneary dodged. Piplup followed with Peck, only for Buneary to dodge again. When Piplup used another Bubble Beam, Buneary countered with Ice Beam. The two moves clashed, creating an explosion. Buneary then used the smoke to surprise Piplup with Dizzy Punch, but he was able to dodge and use Peck, hitting Buneary and nodding to Dawn so she could throw a Poké Ball. After a few seconds, Buneary was successfully caught, joining Dawn on her quest to become a Top Coordinator.
Buneary made its stage debut in Arrival of a Rival!, where it was used in the Battle Round of the Jubilife City Pokémon Contest. It was first seen defeating a Bidoof to advance Dawn to the semifinals. There, it went up against Zoey's Glameow. Their battle began with Buneary using Ice Beam, which was countered by Glameow's Shadow Claw and used to create a stunning contrast that cost Dawn a few points. After that, Buneary used Bounce and Glameow used its curled tail to jump and surprise Buneary with Fury Swipes. Glameow proceeded with Iron Tail, but Buneary managed to stop the attack by using its ears to grab Glameow's tail. Seeing this, Zoey ordered Glameow to spin its tail, making Buneary spin and sending it flying. Buneary fought back with Ice Beam, which Glameow managed to dodge. However, the Ice-type move ended up freezing the stage, making Glameow slip up and allowing Buneary to attack it repeatedly with Dizzy Punch and Bounce. When Glameow was about to be hit by another Dizzy Punch, it used Shadow Claw to break the ice covering the stage, sending shards towards Buneary before using Iron Tail to make it hit the ground. Time ran out after that and Buneary lost the battle on points, eliminating Dawn from the competition.
In Smells Like Team Spirit!, Buneary was used alongside Conway's Slowking in the semifinal round of the Hearthome City Tag Battle Competition. They managed to defeat their opponents and advance their Trainers to the final round.
Buneary was the first Pokémon Dawn sent out during her Gym battle against Maylene at the Veilstone Gym in Crossing the Battle Line!. Dawn was counting on Buneary's jumping skills to defeat Maylene's Fighting-type Pokémon. Going up against Meditite, Buneary started the battle with its Flying-type Bounce attack. However, the Meditate Pokémon used Detect to sense and then avoid Buneary's move, preventing damage. After that, Meditite managed to hit Buneary with its Drain Punch despite its attempt to spin and dodge the attack. Buneary got up and used Ice Beam, freezing Meditite briefly as it used Confusion to break from the ice and direct the shards at Buneary. Thanks to its footwork skills, Buneary was able to avoid the ice shards, but Meditite used Confusion one more time to lift Buneary into the air then toss it down to the ground. By extending its rolled-up ears, Buneary softened the impact before using Bounce. Meditite then used Drain Punch and the two Pokémon clashed in mid-air, causing an explosion and rendering Buneary unable to continue battling.
In Pruning a Passel of Pals!, Buneary was used in the Battle Round of the Wallace Cup. It battled a Wailmer and won, allowing Dawn to advance in the competition.
With Dawn at the Hearthome Collection
In Arriving in Style!, Dawn and Buneary were invited by Paris to register for the Hearthome Collection, a fashion event where Pokémon Stylists show off their Pokémon's best looks. Dawn initially had trouble picking a design for herself and Buneary, but after remembering what Hermione had told her earlier about Poké Stylists and Coordinators being one and the same, as well as Zoey's advice to focus on showcasing the Pokémon as they are always the main attraction, she got inspired and began designing again. The next day, Dawn and Buneary were seen wearing simple snow-themed outfits for the competition. During its performance, Buneary used its Ice Beam attack to create several ice pillars before displaying its jumping ability to the judges. This secured it a spot among the three finalists, along with Ash's Pikachu and Cocoa's Mismagius. After Team Rocket interrupted the competition with their usual antics, Buneary used Bounce together with Paris's Lopunny to destroy their mecha and send them blasting off. Paris later announced Dawn and Buneary as the winners of the Hearthome Collection, congratulating Dawn for using simple accessories to show off Buneary.
Buneary was Dawn's choice for the Appeals Round of the Celestic Contest in Battling The Generation Gap!. She was sent out with a Party Seal and used Bounce to start its performance, jumping up high then spinning in the air. It proceeded with Ice Beam to freeze the stage and create a slide of ice so she could skate on it. After skating across the icy stage for a while, she used Dizzy Punch, allowing it to skate on her ears. However, she lost control of its rapid spinning movements and ended up flying across the hall. Seeing this, Dawn rushed to catch Buneary then told it to smile and pose as a way to make up for their mistake. The performance was praised by the judges, with Raoul Contesta saying it showed off how cute Buneary can be and Nurse Joy commenting how much fun Buneary seemed to be having. As a result, Dawn was allowed to move on to the second round Contest Battles.
In Hold the Phione!, a wild Phione fell in love with Buneary. It became jealous of Pikachu and challenged him to a battle, but Buneary decided to fight instead. During the battle, Phione was able to take advantage of the proximity to the sea and confuse Buneary, but it eventually knocked it out with its Bounce attack. Upon seeing Phione leaving feeling down, Buneary said something to cheer it up, putting a smile on its face.
In Another One Gabites the Dust!, Buneary was used in the Appeals Round of the Chocovine Contest. Its performance, which consisted in creating an ice sculpture to slide on, impressed the judges enough for them to grant Dawn a place in the second round.
When Dawn sent out Buneary in Battling a Cute Drama!, Buneary's cuteness attracted attention from a Trainer in the Shelter Town Pokémon Center. The Trainer, named Marilyn, approached Dawn and asked her for a battle. Dawn accepted the challenge and used Buneary to battle Marilyn's Cherubi. As Marilyn wanted to appreciate Cherubi's cute appearance a little longer, Dawn was the first to make a move, commanding Buneary to use Dizzy Punch. Despite being hit multiple times, Cherubi did not counterattack and so Buneary used Ice Beam. This time, Cherubi used Protect to defend itself but acted as if it was taking damage from the attack. Upon seeing this, Brock interrupted the battle and gave Marilyn a lecture before telling her she would be disqualified if she refused to battle properly. After that, Cherubi fought back by using Magical Leaf. Buneary tried to evade the attack but ended up getting hit. Before Buneary could react, Cherubi used Tackle and then Solar Beam, knocking Buneary out.
At the Daybreak Contest with Piplup
In Yes in Dee Dee, It's Dawn!, Buneary teamed up with Piplup to perform at the Daybreak Town Pokémon Contest, which was being held under the Double Performance rule. Piplup used Bubble Beam to start things off and Buneary followed with an Ice Beam, freezing the bubbles that were floating around the arena. After that, it used Bounce to leap in the frozen bubbles, displaying its footwork and receiving compliments from Marian for doing so. It then used a variation of the technique it perfected in Wild in the Streets! and Piplup did the same while simultaneously using his Peck attack. The two of them finished the performance by popping up the bubbles and sending a shower of sparkles down to the crowd. Their performance received positive reviews from the three judges and allowed Dawn to advance to the Battle Stage.
In Teaching the Student Teacher!, Buneary was called out to help Dawn perfect her newest Contest combination, the Ice Chandelier. It used its Ice Beam to trap Pachirisu in a ball of ice and Pachirisu used its Discharge to make the ice shine brightly. This combination was later used by Pachirisu and Mamoswine in the Grand Festival.
In Last Call — First Round!, Buneary was used in the Performance Stage of the Sinnoh Grand Festival along with Cyndaquil. Both of them were sent out with Line Seals and Buneary used Ice Beam to create a large frozen path resembling a roller coaster. Cyndaquil proceeded with Flame Wheel, rolling over the path and melting a trench for Buneary to slide on. After that, Buneary charged an Ice Beam and Cyndaquil used Smokescreen in order to cloak themselves above a large frozen spike. When the smoke was blown away, Buneary was seen inside a Poké Ball made of ice with Cyndaquil standing on top, impressing the judges and securing Dawn a place among the Coordinators advancing to the Contest Battles. It was later used in Coming Full-Festival Circle!, where it battled along with Cyndaquil against Jessilina's Seviper and Carnivine in the semifinals of the competition. Together they managed to defeat their opponents and advance Dawn to the final round.
It was revealed in Memories are Made of Bliss! that Buneary had been chosen by Hermione to be a model of the Poké Chic magazine. As a result, Dawn decided to remain in the Sinnoh region while Ash and Brock returned to Kanto.
In SS024, it was used to help fight off the Ariados that were attacking Dawn and Shinko. It was caught in String Shot and couldn't do anything until Cyndaquil evolved into Quilava and saved it.
In Piplup, Pansage, and a Meeting of the Times!, Buneary was introduced to Ash, Iris, and Cilan's Pokémon. It was initially shy about seeing so many unfamiliar faces, but upon seeing Pikachu, it quickly embraced him, much to Oshawott's disappointment.
Buneary often displays traditional feminine traits similar to its Trainer. It enjoys dressing up in beautiful outfits and showing off in them, particularly to Pikachu. It began wearing a vest with a heart on it in The Bells Are Singing!, which was designed by Dawn and sewed by Johanna. It appears to be very proud of its vest and, for the most part, only takes it off to compete in Pokémon Contests.
Buneary has been shown to be a helpful Pokémon. For instance, in Doc Brock!, it took off its vest to give to Pachirisu when the Electric-type Pokémon was sick from storing too much electricity. It also used Ice Beam to make an ice pack for Pachirisu in order to bring its fever down.
Buneary's affection towards Pikachu
Buneary developed a crush on Pikachu after it spotted him grabbing a potato that Brock's Croagunk had tossed in the air. It is shown to be sensitive whenever Pikachu gets frustrated with its acts of affection at times that don't call for it. When around Pikachu, it gets flustered and hides its face in its fur. However, it is always cheering for Pikachu when he participates in Gym battles and, when not being used itself, for Dawn during Contests.
Buneary has shown time after time that it was meant to compete in Contests, using its moves in unique ways that make it more noticeable such as making an ice slide from Ice Beam as an appeal. Commonly it combines Ice Beam with spinning and sliding actions when performing in a Contest.
Despite her size, Buneary is very powerful and was able to tire out Maylene's Meditite enough so that Ambipom could defeat it. Its Ice Beam, which appears to be its main attack, is powerful enough to freeze an entire lake.
Upon its return in Unova with Dawn and the others, it was shown to be quite shy, hiding behind Mamoswine when everybody was introducing each other's Pokémon. However, upon seeing Pikachu, a face it did recognize, it quickly embraced him.