Empoleon first appeared along with Barry in Barry's Busting Out All Over! where it was revealed to be a strong Pokémon in a battle against Ash's Pikachu. However, after a hard-fought battle, it lost the match.
In A Shield with a Twist, it was revealed that Empoleon had trained with Barry in Iron Island before they defeated Byron. It also appeared in Jumping Rocket Ship where it got separated with Brock's Happiny, Dawn's Piplup and Ash's Grotle.
It appeared again in Steeling Peace of Mind! with Barry and was one of the victims of Team Galactic's tampering on Iron Island due to it being part Template:Type2. It appeared in Saving the World From Ruins! with its Trainer, bidding Ash and co. a farewell. It appeared again in Stopped in the Name of Love! alongside Barry.
In To Thine Own Pokémon Be True!, it competed in the Pokémon Ping Pong Tournament together with Barry. They were both defeated by O and his Shiftry.
In Challenging a Towering Figure!, it was used in the Twinleaf Festival in the Battle Tournament, but soon lost to Ash's Pikachu once again.
It fought Ash's newly obtained Gible in Gotta Get a Gible!, where it won, giving Barry his first victory over Ash. It appeared again in Fighting Ire with Fire!, where it battled Ash's Monferno.
Empoleon's next appearance came in DP183, where it got Barry through the preliminaries of the Suzuran Conference after defeating another trainer's Nosepass. In DP184 it was used in Barry's battle against Paul.
