In Safari Zone, Ian found Venomoth in the Safari Zone. It escaped the first two times he tried to catch it, until Ian rode on a Tauros to chase after it. He managed to capture it on the third try.
Venomoth is kept in its Safari Ball, and its revealed that Ian added Venomoth as his sixth member to his party.
In Vs. Gloom, Venomoth is Ian's second choice to fight Erika. Its abilities to keep Weepinbell at a distance allowed it to win. It was defeated by her Gloom, unable to take the smell.
In Vs. Primeape, Venomoth is Ian's trump card against the wild Primeape. Its Stun Spore and psychic attacks allowed Ian to weaken Primeape enough to catch it. After this, Ian replaced Venomoth in his party with Primeape.
In Vs. Bellsprout, Venomoth was added to Ian's party in his battle against Jeanette Fisher, and was his final Pokémon used. It managed to defeat her Bellsprout, winning him the match.
In Vs. Battle Tower 2, Venomoth is Ian's ace against Anabel's Espeon. Due to the Inverse Battle, it resists Espeon's Psychic, and deflects Espeon with its own Psychic. Espeon tried to paralyze Venomoth with Zap Cannon, but Venomoth's Shield Dust ability protected it. When Venomoth paralyzes Espeon with Stun Spore, its Synchronize affects Venomoth. Anabel is forced to destroy the Inverse Battle panels. Venomoth then defeats Espeon with Silver Wind.