Barry's Busting Out All Over! (Japanese: ライバルトレーナー・ジュン登場！！Enter Rival Trainer Jun!!) is the 101st episode of the Diamond & Pearl series, and the 567th episode of the Pokémon anime. It first aired in Japan on November 6, 2008 and in the United States on April 11, 2009.
As Ash enters the Hearthome Gym for his Gym Challenge, he collides with a blond Trainer in a hurry! The Trainer races off down the street, leaving his badge case behind. Then Fantina emerges from the Gym and explains that she's been battling all day—the blond Trainer was her latest (unsuccessful) challenger, and her Pokémon need a break. Ash's battle will have to wait until tomorrow, so he heads to the Pokémon Center and runs into the mystery Trainer yet again.
The Trainer's name is Barry and Paul is his personal idol. With taste like that, he rubs Ash and his friends the wrong way—then challenges Ash to a battle, too. But Barry left his Poké Balls in storage at a very suspicious-looking stand in the middle of town. Fantina stops by on her way to the store, and she even thinks there's something odd about this new Pokémon storage. Sure enough, it's all a Team Rocket scam! But between Fantina, Barry, and our heroes, Team Rocket doesn't stand a chance. When James hears Barry and his Empoleon even beat Gardenia, he's happy to hear that Gardenia taught Drain Punch to his Cacnea. The news makes blasting off much more bearable!
With Team Rocket out of the picture, Barry and Ash can finally battle. Like Paul, Barry believes that finding strong Pokémon is the key to victory—he's not interested in bonding with his Pokémon. The true test will be his 3-on-3 battle with Ash, however. First up, Barry's Staraptor vs. Ash's Chimchar. Chimchar uses Dig to dodge Staraptor's attacks, then knocks it out. Barry's Roserade defeats Chimchar, but Gliscor goes hand-to-hand with Roserade for a double knock-out! Now Pikachu takes on Empoleon, and the bond between Ash and Pikachu helps them come back from behind to beat Empoleon with Electric-type attacks. Barry isn't impressed, but he's willing to stick around and see Ash's Gym challenge tomorrow—which means Ash can't afford to lose against Fantina!
Ash and his friends have returned to Hearthome City for Ash's fifth Gymbattle. Ash runs off to the Hearthome Gym excited as his friends follow. As Ash steps up to the Gym's front doors, someone on the inside opens the door on Ash, knocking him and Pikachu down the stairs. The Trainer also fell and manages to get up in a hurry, criticizing Ash as if it were his fault before proclaiming himself as a powerful Trainer and running off almost immediately. Pikachu notices a Badge case that the guy dropped and Ash retrieves it, noticing three Badges inside. As his friends finally catch up to him, Fantina steps out and greets him, noticing the Badge case that her previous challenger was holding, mentioning that he came from Twinleaf Town, the note getting Dawn's attention. Ash is quick to ask for his official battle, but her Pokémon have to rest after battling, putting off the duel for the next day and upsetting Ash.
Ash and his friends decide to head to the Pokémon Center to rest as well. The same Trainer Ash saw at the Gym runs straight into Ash again, both getting knocked down. The Trainer notices his Badge case and reclaims it, think Ash stole it, but he suddenly recognizes Ash from the Hearthome City Tag Battle Competition, battling with Paul and labeling Ash as weaker than Paul, which irritates Ash. Dawn suddenly remembers who the Trainer is, identifying him as Barry, remembering him from a former duet with an Exploud in the Twinleaf Festival, but Barry doesn't know Dawn. Suddenly, he also associates her from the Hearthome battle, terming her as the "hopelessly geeky" Trainer that lost to Paul, which irritates her as well. Brock mentions that he was in the battle, but Barry doesn't know him either. He reverts to snubbing Ash for his inferiority to Paul. Ash identifies himself to Barry and challenges him to a battle, but Dawn spots Barry's new Pokétch. He discusses how he got it before getting frantic and blaming Dawn for going off topic about the battle.
Ash sends out Chimchar, which Barry immediately recognizes it as Paul's and thinks that Ash traded to get it. Even after Ash mentions that Paul abandoned it, Barry refuses to believe Paul abandoned it and thinks Ash wants to become as strong as Paul, which Barry is also trying to do. Barry gloats about getting three Badges, but Ash mentions that he has four, which slightly stuns Barry, but he still believes he's stronger. Barry tries to summon a Pokémon to battle, but he realizes that he left his Poké Balls in storage, running off to get them as Ash follows.
Meanwhile, Team Rocket sets up a fake Storage System booth, their real goal being to steal Trainers' Pokémon. They prepare to leave when Barry shows up to reclaim his Pokémon. Team Rocket heads into the back as Brock notices something amiss. Fantina shows up and also notices something fishy. The booth falls away as Team Rocket tries to escape in their balloon, reciting their motto, but Barry cuts them off. Ash sends out Gliscor and James sends out Carnivine, which promptly latches onto him, forcing Jessie to deploy her Seviper. Fantina sends Mismagius to use Psybeam, stopping and confusing Seviper. Gliscor uses X-Scissor to pop the balloon and send it crashing to the ground.
The bag of Poké Balls lands nearby, Barry quickly searching for his Poké Balls and quickly finding them. Seviper and Carnivine charge but Piplup and Pikachu race forward. Carnivine's Bullet Seed stalls the duo as Seviper lunges forward with a Biteattack. Barry summons his Empoleon and uses Hydro Cannon to blast Seviper back. He shows off that Hydro Cannon helped him beat Gardenia and earn the Forest Badge, mentioning how powerful her Cacnea was. James knows that the Cacnea Barry mentioned was his, amazed that it mastered Drain Punch, and rushes to Barry, asking more questions about Cacnea. Meowth and Wobbuffet drag him away as Team Rocket prepares to attack again, Carnivine using Bite and Seviper using Poison Tail. Piplup uses Bubble Beam and Pikachu uses Thunderbolt to send them back as Empoleon uses Hyper Beam to send Team Rocket blasting off.
Fantina takes the job of giving the Pokémon back to the Trainers as she looks forward to her next battle with Ash, applauding his improved battle performance. Barry follows Ash and the group as Ash prepares for his battle, Barry also wanting to prepare. Barry states that if his Empoleon isn't strong enough he will simply find more powerful Pokémon, similar to Paul's ideology. Ash stops and questions his thinking, mentioning that cooperative training and bonding is important to growing as a Trainer, which Barry doesn't recognize. Barry acknowledges his impatience, wanting to be as strong as Paul as quickly as possible. As Barry is aspiring to be similar to Paul, it irritates Ash more. Dawn mentions that Ash battled Paul several times. When Barry makes fun of Ash not being able to defeat Paul, Ash's temper flares again, and Barry decides to battle Ash.
At the Pokémon Center, Brock officiates the three on three battle. The first round pits Ash's Chimchar against Barry's Staraptor. Staraptor uses Tackle as Chimchar dodges and fires Flamethrower. Staraptor dodges and comes around to use Close Combat. Chimchar dodges most of the strikes, but Chimchar takes a few hits and gets thrown back. Staraptor charges with Wing Attack, but Chimchar uses Dig to escape before coming up and using Flamethrower to knock out Staraptor.
Barry sends out Roserade and uses Poison Jab to knock Chimchar back. Barry orders multiple Poison Jabs as Chimchar dodges. However, Roserade uses its legs to lower Chimchar's guard and managing to get in clean strikes, eventually knocking out Chimchar with one powerful strike. Ash sends out Gliscor, striking with X-Scissor. Roserade uses Poison Jab to block. Both Pokémon use their attacks to strike and block continually. Barry tells Roserade to keep attacking as both Pokémon stop defending and go for complete offense, eventually winding up with both Pokémon knocked out.
Knowing that this battle will determine his chance of winning against Fantina, Ash pits Pikachu against Empoleon. Pikachu charges with Thunderbolt as Empoleon uses Hydro Cannon to block. Pikachu dodges the blast as Empoleon rushes with Steel Wing, Pikachu countering with Iron Tail. Empoleon uses Steel Wing again as Pikachu repeats Iron Tail. Pikachu lands a few hits before getting knocked back. Empoleon fires Hyper Beam as Pikachu gets hit, flying up in the air, seemingly defeated. Ash's plea for courage snaps Pikachu back to action, ready to continue. Knowing that Empoleon is vulnerable after firing Hyper Beam, Pikachu hits with Thunderbolt, knocking Empoleon down before Pikachu follows up with Volt Tackle, knocking out Empoleon and giving Ash the win. Pikachu hugs Ash as Dawn and Brock congratulate him. Barry, stunned at losing to Ash, sinks to his knees but quickly shaking it off, thinking Ash got lucky and that he is still stronger. Ash tells him to watch his battle against Fantina. The next day, Ash enters the Hearthome Gym for his next battle.
Interestingly, while Ash's Badge case has all eight places shaped ready for the Badges he will eventually receive, Barry's Badge case has at least one space different as he has a Badge that is not present in the games, which shows that there are at least nine Gyms in Sinnoh.