Raichu first appeared when she was introduced to Ash, Serena, and Bonnie. Unfortunately, Raichu, along with her dancing partner Wartortle and Ash's Sliggoo, were captured by Team Rocket. They managed to escape after Jessie's Pumpkaboo use Shadow Ball to knock the cage over a cliff and shattering it to pieces. Tierno and Bonnie arrived and found them, but when they confronted Team Rocket, they started a forest fire by accident. Sliggoo bravely used Rain Dance to douse the fire and surprisingly evolved into Goodra. Goodra then blasted Team Rocket off with its newly-learned Dragon Pulse move. Raichu tag-teamed with Wartortle in a double battle against Ash's Pikachu and Goodra. Raichu used Charge Beam on Goodra, who used Bide, absorbing the attacks. Raichu used Focus Blast, attacking Goodra, who still absorbed the attacks. Raichu repeated the attack, which hit Goodra, who fired Bide, hitting Raichu and Wartortle, nearly defeating them. Raichu tried to use Focus Blast to free Wartortle, who was grabbed by Goodra, but Goodra threw Wartortle onto Raichu, canceling the attempt. Pikachu used Thunderbolt and Goodra used Dragon Pulse, defeating Raichu and Wartortle.
Raichu battled at the Lumiose Conference against Sawyer, after Tierno's Ludicolo was defeated. Sawyer's Aegislash started with Slash, but Raichu used Dig, allowing her to dodge the attack and defeat Aegislash with the same move. Next, Sawyer sent Slurpuff, who immediately used Attract. This caused Raichu to be infatuated and ignore Tierno's command to use Charge Beam. Slurpuff easily damaged Raichu with Energy Ball, so Tierno called Raichu back. Later on, once Tierno's Blastoise got defeated, he sent Raichu back to battle Sawyer's Sceptile. Raichu was to use Thunder, which, due to the rain caused by Tierno's Blastoise's Rain Dance, made it an unmissable move. However, Sawyer Mega Evolved his Sceptile, who, despite being electrocuted, took no damage, due to Mega Sceptile's Lightning Rod ability. Raichu attempted to use Focus Blast, but was defeated by Mega Sceptile's Dragon Claw attack.