Electivire first appeared when Ash returned to Pallet Town after becoming the master of the Battle Frontier. Electivire battled Ash's Pikachu and easily won. It then traveled with Gary back to Sinnoh and was used to help in Gary's studies with Professor Rowan.
Electivire also appeared to help Gary and Ash sabotage Pokémon Hunter J's ship. Its final appearance was when it battled Saturn's Toxicroak alongside Gary's Umbreon. Toxicroak's superior speed and power allowed it to defeat both Electivire and Umbreon, a remarkable feat considering they were among Gary's most powerful Pokémon.