As a Poliwag, it was very friendly and cheerful, and likes to help people. This was demonstrated in the episode, The Stun Spore Detour. After it evolved into a Poliwhirl, it was shown as very strong and determined Pokémon and Misty began to use it in many battles, as it became a very strong Pokémon. Poliwhirl also had a bit of a confidence problem as shown in Hook, Line, and Stinker when Poliwhirl would hide behind Misty when overwhelmed.
After evolving into Politoed in Outrageous Fortunes, it is always very happy and loves to clap and is very cheerful, enthusiastic, and eager to please. In I Politoed Ya So!, it takes up cheerleading. Even when Misty screams at it for being distracted during a battle, Politoed is always happy and if someone is sad it can cheer them up with applause. It also cheers for Ash during the Silver Conference.
In The Stun Spore Detour, Misty befriended a Politoed as a Poliwag during her travels through the Orange Islands when she was searching for the antidote called the Salveo Weed to cure both Ash and Tracey's paralysis from Vileplume's Stun Spore. When James and Meowth attempt to get it for the second time after Misty defeats them the first time, Poliwag manages to hit James' Weezing with a Double Slap from its tail to knock it, James and Meowth down to the hill. In the end, Poliwag eventually joins in Misty's side and it accompanied her travels in Johto.
In The Totodile Duel, during a battle against Ash and his Bulbasaur, Poliwag was knocked down from Bulbasaur's Razor Leaf as it evolved into a Poliwhirl but is still defeated by Bulbasaur. Poliwhirl is mostly used by Misty even in the Whirl Cup.
In Outrageous Fortunes, after Poliwhirl was defeated by Delaney's Poliwrath, Brock stops the match due to its injuries and exhaustion during its fight against Ash's Bayleef. When Ash slips on the floor and his belongings are flying out on his backpack, it drops the King's Rock as Poliwhirl takes it before Misty returns it to its Poké Ball to heal its injuries at the Pokémon Center. When they save Delaney's Poliwrath from Jessie's control, Misty releases Poliwhirl to take on Team Rocket as Poliwhirl finally wore the King's Rock and it activates to evolve into a happy-go-lucky, Politoed as Ash states it was pretty weird when it looked it up on the Pokédex and Misty stating that her Politoed is very cute. Upon fighting against James' Victreebel, Politoed tried to befriend it by shaking hands making Misty corrects her Pokémon that it was the enemy and she convinces it to use all of Poliwhirl's attacks after it's evolution as it demonstrates its Water Gun and Double Slap and later uses a new move Swagger to make both Pokémon confused until Jessie's Arbok manages to tackle it. Together, both Delaney's Poliwrath and Misty's Politoed defeat both Jessie's Arbok and James' Victreebel using their Double Slap before being hit by Ash's Phanpy's Take Down and getting blasted off by Pikachu's Thunderbolt.
In I Politoed Ya So!, Politoed learns to do cheerleading by Tammy when she replaces her Politoed nicknamed Bean for all of her Pokémon for the cheerdancing competition. As all of Tammy's Pokémon are crying due to Tammy's scolding and her pride of winning the competition, Politoed claps happily to cheer them up and Tammy became apologetic to her Pokémon after seeing Misty shows her caring side to her Politoed. When Team Rocket captures everyone with their robot, Politoed teams up with Bean by defeating their Pokémon and washes it with their Water Gun allowing Pikachu to shock the drench robot with Thunderbolt to blasts them off. Politoed's cheerleading skills are also used to cheer Ash when he competes at the Silver Conference.
In Great Bowls of Fire!, Politoed is teaming up with Misty's Staryu to put out the forest fire with their Water Guns in the Dragon Holy Land and later extinguishes the burning Dragon Shrine with its Water Gun.
In Cerulean Blues, Politoed is last seen being released by Misty while trying to restrain her Gyarados along with Psyduck who is aquaphobic but failed and Politoed was seen clapping happily when Misty got washed up from Gyarados' Hydro Pump until it obeys her when she saves her Corsola from Tentacruel's Poison Sting.
Politoed is now currently resides in the Cerulean Gym with Misty.
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At Cerulean Gym