Bianca's Minccino first appeared in Minccino—Neat and Tidy!, where he stole a Badge case that Bianca was delivering to Ash, in order to clean it. Bianca, thinking that Minccino was extremely cute, sent out her Pignite to battle him in the hopes of capturing him. He was able to dodge some of Pignite's powerful moves and used Hyper Voice and Tickle, and Pignite had to be returned. Ash was about to send his Pikachu to battle the Minccino when Oshawott came out of his Poké Ball to battle him instead. Minccino dodged Oshawott's Tackle and evaded his Razor Shell before defeating him with a combination of Tickle and Double Slap. He then proceeded to run away, with Ash's Badge case in tow.
Bianca then tried tempting Minccino with a cloche and a dirty spoon that she "borrowed" from Cilan which seemed to work, but Minccino just carried the cloche away, much to Cilan's dismay. They found where Minccino was hiding and Ash sent out Snivy, who used Attract, but Minccino used Attract back, forcing Ash to recall Snivy. This also confirmed that Minccino was male, as his Attract worked on Snivy, who was female. Pikachu battled last, and the pair seemed to be equally matched. Minccino used his Tickle-Hyper Voice combination, but Pikachu used Thunderbolt, which dazed Minccino. Bianca then managed to catch him when he attempted to clean her dirty Poké Ball.
Bianca called upon Minccino's help in Emolga the Irresistible! where she wished to catch an Emolga. He seemed to be gaining the upper hand when Emolga suddenly attacked with Discharge. Both Pokémon used Attract on each other and the two attacks clashed until Emolga's pushed through. He would have been affected by it but Oshawott jumped in the way and took the hit for him. In Emolga and the New Volt Switch!, he battled the same Emolga which was now under the ownership of Iris. When he was gaining the upper hand, she used Volt Switch and swapped places with Cilan's Pansage who was in the middle of taking a nap in his Poké Ball. He was angered when he was hit by Minccino's Hyper Voice and knocked him out with a single Solar Beam.
In Cilan Versus Trip, Ash Versus Georgia!, Bianca used Minccino in the Club Battle tournament. He went up against Stephan's Zebstrika. Despite putting up a good fight, he was defeated by a powerful Stomp attack, knocking Bianca out of the tournament.
Bianca used Minccino against Elesa for her Gym battle in Enter Elesa, Electrifying Gym Leader!. Like Shelmet before him, Minccino was quickly defeated by Elesa's Zebstrika, even with his newly learned Swift attack.
Minccino was revealed to have learned Thunderbolt in Crisis at Chargestone Cave!. Bianca ordered him to use his new move on a tree to lure a group of wild Galvantula away and to use Swift, which knocked some Oran berries out of the tree and onto the Galvantula, knocking them out briefly. Minccino and Pikachu were soon wrapped up by Galvantula's String Shot and taken from their Trainers to Galvantula and Joltik's nest. The two Pokémon were told that the Joltik needed to absorb electricity in order to built up their strength, so they both helped them out by using Thunderbolt on them. Later, Minccino joined Cilan's Dwebble, Iris's Excadrill and Pikachu in battling Team Rocket.
Minccino made a cameo appearance in Let's Join Hands.