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. She managed to rescue Pikachu and stayed near the group's campsite after that, but Brock's Croagunk noticed she was hiding in the bushes and she 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 and 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 she acted completely different than when battling Piplup before, covering her face with her fur. She then froze Ash, Dawn, and Brock with Ice Beam and started dancing with Pikachu. Pikachu later scolded Buneary for her actions, upsetting her and making her cry. Buneary stopped crying when she heard something. However, this did not prevent her 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 she would like to travel with Dawn. She 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 her stage debut in Arrival of a Rival!, where she was used in the Battle Round of the Jubilife City Pokémon Contest. She was first seen defeating a Bidoof to advance Dawn to the semifinals. There, she 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 her with Fury Swipes. Glameow proceeded with Iron Tail, but Buneary managed to stop the attack by using her ears to grab Glameow's tail. Seeing this, Zoey ordered Glameow to spin its tail, making Buneary spin and sending her 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 her 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 her 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 her 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 her footwork skills, Buneary was able to avoid the ice shards, but Meditite used Confusion one more time to lift her into the air then toss her down to the ground. By extending her 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. She battled against 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 her performance, Buneary used her Ice Beam attack to create several ice pillars before displaying her jumping ability to the judges. This secured her 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 her performance, jumping up high then spinning in the air. She 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 her to skate on her ears. However, she lost control of her rapid spinning movements and ended up flying across the hall. Seeing this, Dawn rushed to catch Buneary then told her 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 she eventually knocked it out with her 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. Her 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 counter attack 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, she used Bounce to leap in the frozen bubbles, displaying her footwork and receiving compliments from Marian for doing so. She then used a variation of the technique she 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. She used her 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. She was later used in Coming Full-Festival Circle!, where she 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, she was used to help fight off the Ariados that were attacking Dawn. She was caught in String Shot and couldn't do anything until Cyndaquil evolved into Quilava and saved her.
In Piplup, Pansage, and a Meeting of the Times!, Buneary was introduced to Ash, Cilan and Iris's Pokémon. Upon seeing Pikachu, she quickly embraced him, much to Oshawott's disappointment.
Buneary often displays traditional feminine traits similar to her Trainer. She enjoys dressing up in beautiful outfits and showing off in them, particularly to Pikachu. She began wearing a vest with a heart on it in The Bells Are Singing!, which was designed by Dawn and sewed by Johanna. She appears to be very proud of her 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!, she took off her vest to give to Pachirisu when the Electric-type Pokémon was sick from storing too much electricity. She 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 she spotted him grabbing a potato that Brock's Croagunk had tossed in the air. She is shown to be sensitive whenever Pikachu gets frustrated with her acts of affection at times that don't call for it. When around Pikachu, she gets flustered and hides her face in her fur. However, she is always cheering for Pikachu when he participates in Gym battles and, when not being used herself, for Dawn during Contests.
Buneary has shown time after time that she was meant to compete in Contests, using her moves in unique ways that make her more noticeable such as making an ice slide from Ice Beam as an appeal. Commonly she 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. Her Ice Beam, which appears to be her main attack, is powerful enough to freeze an entire lake.
Upon her return in Unova with Dawn and the others, after becoming embraced with Pikachu, she was shown to be quite shy, hiding behind Mamoswine when everybody was introducing each others' Pokémon.