Serperior was first introduced as a Snivy in Professor Juniper's lab, where he was chosen by Trip as his starter Pokémon in In The Shadow of Zekrom!. Shortly after obtaining him, Trip challenged Ash to a Pokémon battle and used Snivy against Ash's Pikachu. As Pikachu was unable to use Electric attacks due to an encounter with Zekrom, Snivy was able to defeat him easily.
Prior to Triple Leaders, Team Threats!, Snivy was shown to have already evolved into a Servine, when Ash challenged Trip to another Pokémon battle in a Battle Club in A Rival Battle for Club Champ!. He quickly defeated Ash's Pikachu again with his Cut. During the battle with Ash's Snivy, he was revealed to be male when he became infatuated with her after being hit by her Attract. As Servine was unable to attack, he was quickly defeated by her.
It was revealed by Cilan that Servine defeated Chili's Pansear in Trip's battle for the Trio Badge.
Servine appeared again in Ash and Trip's Third Battle! in Trip's 3-on-3 battle with Ash. He once again battled with Ash's Snivy, this time, however, he effectively stopped Snivy's Attract with a Leaf Tornado and came out victorious with one powerful Cut attack.
In BW090, Servine was shown to have evolved into a Serperior and was used by Trip in the Pokémon World Tournament Junior Cup. In the first round, it went up against Burgundy's Darmanitan and managed to freeze it in place with a Leer. Then, it easily knocked it out with a powerful SolarBeam, giving Trip the win.
In BW091, Serperior battled Marufuji's Heatmor in the second round and won. In the same episode, Serperior battled Cilan's Crustle in the semifinals and defeated it with Frenzy Plant, giving Trip the win.
In BW092, Serperior battled Ash's Pignite in the finals and won, revealing it had learned another new move, Dragon Tail, in the process.