Barry made his debut appearance in Barry's Busting Out All Over!, where he was intended to challenge Fantina for a Gym battle, but coming up with Ash at the door of the Gym. He then challenged Ash to a battle to prove his training methods wrong, but Ash came out as the victor.
After Ash defeated him, Barry stayed to watch Ash challenge Fantina in A Shield with a Twist!. At times, Barry was skeptical about Ash's strategy in the battle, but by the end of the fight, he realized that his techniques were excellent. He later stated that he would be his rival if Ash could defeat Byron, whom Barry had previously beaten.
After staying with the group for the following episode, he departed to train at Iron Island, but appeared again in Steeling Peace of Mind! and Saving the World From Ruins! at Iron Island, where after being caught up in Team Galactic's plot to use the island as a radar to scan for the Spear Pillar he and Ash put aside most of their differences and became friendly rivals. He also appeared in Stopped in the Name of Love! where he wanted to enter the Pokémon Ping Pong Tournament, which he later loses in To Thine Own Pokémon Be True!. It is also revealed that he is good friends with Dawn's rival, Kenny. He also appeared in Old Rivals, New Tricks! watching Dawn and Kenny participate in the Contest held inSandalstraw Town.
Barry appeared again in Historical Mystery Tour! where he then decided to have a battle with Ash, which was soon interrupted. He bumps into his father, Palmer at the end of the episode. In Challenging a Towering Figure!, he entered the Battle Tournament as part of the Twinleaf Festival in the hope that he would get to battle Palmer, but soon lost to Ash.Barry reappeared in Gotta Get a Gible!, where he battled Ash and his newly-caught Gible. Barry wins his first battle against Ash, but Ash doesn't take it harshly, praising Gible anyway and instructing it to listen next time. Barry celebrates his win as he holds up his ticket to challenge Fantina, but Gible bites his hand and eats the ticket.
Barry once again appeared in Fighting Ire with Fire!, along with Paul where he challenged his idol to a battle, but to his dismay, Paul refused. Barry then battled Ash once again, using his Empoleon against Ash's Monferno. However, the battle was put on hold when Team Rocket attacked.
In An Old Family Blend!, Barry showed up for the Lily of the Valley Conference where he was seen in the stadium along with all the other competitors. InLeague Unleashed!, he passed the preliminary round. In Casting a Paul on Barry! he battled his idol Paul in the third round of the Lily of the Valley Conference, and even though he put up a strong battle, utilizing two new Pokémon in his team, Skarmory and Hitmonlee, along with his partner, Empoleon, he ended up falling before the superior strength and tactics of Paul and his team. He then stayed and watched Ash's battles with Paul and Tobias, and he parted from the group in The Semi-Final Frontier! promising to be reunited with Ash and become as strong as him.
Barry made a cameo appearance in Zoroark: Master of Illusions.