Paul had it as an Elekid during his first appearance in When Pokémon Worlds Collide!. He used it in a battle against Ash and his Pikachu. After a fierce battle, both Pokémon fainted and the battle ended up in a draw. In Paul's Glory Blaze! flashback, it was seen with Paul capturing his Ninjask, shortly before he caught Chimchar.
Electabuzz rejoined Paul after the events of Enter Galactic!, to have the upper hand in the battle against the Pastoria Gym Leader. In Chim - Charred! it was seen helping Paul battle a wild Drapion. It still seemed to have friendly feelings towards Pikachu.
In DP184, during Paul's battle against Barry, Electabuzz was revealed that it had evolved into an Electivire, and had learned Giga Impact prior to the battle. It fought, and won, against Barry's Empoleon. Paul used it as his last Pokémon in his quarter final battle against Ash in DP188 where it defeated Ash's Gliscor and Pikachu using its Motor Drive ability and extensible tails. After a heated battle, it was finally defeated by Infernape once Infernape activated its Blaze ability.
It is one of the two Pokémon Paul has that is voiced by Kenta Miyake, the other being Ursaring.
It is the only one of Paul's Pokémon to evolve onscreen, when it evolved into Electabuzz in Smells Like Team Spirit!
Electivire seems to be the principal rival for Ash's Infernape. They were both introduced together and used in Paul's first gym battle; Electabuzz evolved from Elekid in a double battle partnered with Chimchar, who had only just joined Ash's team. Later, Electabuzz defeated the newly-evolved Monferno in the final round of Ash and Paul's full battle in Evolving Strategies!, and was present for Monferno's final evolution in Fighting Ire with Fire!. This is further proven in DP188 where it battled Infernape in the final round of Ash and Paul's full battle at the Sinnoh League.
Electivire is the only Pokémon Paul used in his battle against Ash in the Suzuran Conference that only has one type.
Paul's Electvire is the first Pokémon in the anime to use more than one ability.