BioBarry is one of Ash's rivals that he met in the Sinnoh region.
Barry bumped into Ash when he was chasing after Gible in a town near Daybreak Town. It was then revealed that he had already won six badges and had also gotten a priority ticket in order to challenge Fantina. He had gotten a bike too, in order to be able to travel from town to town faster, but Ash's Gible (who was still a wild Gible at the time) ate it while he was talking with Ash. Then, furious that he lost his bike, Barry called upon his Empoleon to battle it so that he would be able to catch Gible in the end. A powerful Hydro Cannon attack coming from Barry's Empoleon, though, sent it flying, thus ruining Barry's attempt at a capture. Barry later appeared and challenged Ash to a battle, after seeing that he had managed to catch Gible before him. Barry chose his Empoleon and Ash chose his newly-caught Gible. Due to Barry's Empoleon being overall stronger than his opponent and Gible's disobedience towards Ash during the fight, Barry managed to score a win over Ash.
Ash and his friends encountered Barry again on their way to Sunyshore City. Barry informed Ash that he had already gathered eight badges and, thus was eligible to take part in the Sinnoh League. At the town's Pokémon Center, Barry met Paul for the first time and he challenged him to a battle. Paul refused to battle him, saying that he was in the middle of adjusting his team for the upcoming Sinnoh League, and a battle would distort their condition. He told Barry that he should challenge Ash to a battle instead. Even though he didn't consider the idea at first, as he didn't deem Ash to be on the same level with him due to having only seven badges, he decided to challenge him to a battle after hearing his explanation concerning what had happened between him and Paul, and seeing how determined he was to win the next battle against him.
The first Pokémon Barry chose for his three-on-three battle against Ash was his Empoleon, while Ash chose his Monferno. During the battle, Ash's Monferno was hit by a powerful Hydro Cannon attack and blasted off into the nearby forest. As Ash was calling out to it, Team Rocket suddenly appeared and managed to trap Ash and the others, as well as capture Pikachu, Dawn's Piplup and Barry's Empoleon shortly afterwards. In the end, with the help of Paul's Electabuzz, who aided in stopping Team Rocket's destroyed mecha from collapsing and injuring the captured Pokémon, and Ash's Infernape, who had just evolved unexpectedly from his Monferno, Barry was reunited with his Empoleon.
Barry's Empoleon is Barry's main Pokémon. Barry's Empoleon also appeared when Barry wanted to battle Ash's Gible (who was still a wild Gible at the time) so that he could catch it in the end.One of its powerful Hydro Cannon attacks, though, sent it flying, thus ruining Barry's attempt at a capture. [View More]
Jun's Heracross was first seen on Iron Island training with Jun's Empoleon.
Jun's Staraptor was first seen during a three on three battle with Ash.
Jun's Roserade was first seen during a three on three battle with Ash.
Barry sent out his Skarmory as his first Pokémon to battle against Paul during their battle at the Sinnoh League. It was quickly defeated by Paul's Magmortar as it had the type advantage.
Barry's Hitmonlee was revealed during the battle with Paul at the Sinnoh League. After his Empoleon defeated Magmortar, Barry sent out his Hitmonlee to face Ursaring. Ursaring proved to be a strong opponent and was able to eventually defeat Hitmonlee.