In The Stun Spore Detour, Ash and Tracey were paralyzed by a Vileplume's Stun Spore attack. Misty was left to fetch the cure, Salveyo weed, a special type of aquatic plant found at the bottom of lakes on which Poliwag feed. A friendly wild Poliwag helped her gather the special plant. Poliwag obviously liked Misty because it insisted on coming along with her, and Misty added it to her team. As a Poliwag, it was rarely used because of how clumsy it was on land.
In The Totodile Duel, Ash and Misty both used Lure Balls on a wild Totodile. The Balls caught the Pokémon out of sight, so Ash and Misty had a tournament to see who got the Water-type. During a battle against Bulbasaur, Misty's Poliwag evolved into Poliwhirl. Although Misty still lost, she concluded that she preferred the Poliwhirl who was willing to evolve to help her rather than the Totodile that essentially did whatever it wanted.
In Hook, Line, and Stinker, Misty used Poliwhirl in the Seaking Catching Competition. During the competition, Misty and Poliwhirl formed a rivalry with Andreas and his Poliwrath. Poliwhirl and Misty managed to hook a Seaking just as time ran out for the competition. Both Andreas and Misty had a 55 kilogram Seaking, meaning they had to battle each other to decide the winner. The battle started with Poliwhirl getting overwhelmed due to battling its evolved form. It lost its confidence and hid behind Misty. Misty's Psyduck, Staryu, and Goldeen then popped out of their Balls to encourage Poliwhirl and it decided to resume the match. Poliwhirl then beat Poliwrath, winning the competition for Misty.
Misty used Poliwhirl in the second and third rounds of the Whirl Cup in The Perfect Match!. In the second round Poliwhirl went up against Ash's Totodile. Ash started the battle by having Totodile use Water Gun, but Poliwhirl dove underwater to evade it. Poliwhirl jumped out of the water and attacked with Bubble, dazing Totodile for a while. Poliwhirl attempted to use Double Slap, but Totodile dodged and headbutted it back into a pillar. However, Poliwhirl kicked off the pillar and dove towards Totodile, using Double Slap again, and knocking Totodile out. Ash recalled Totodile and sent out Kingler. Misty again commanded Poliwhirl to unleash another Bubble, but Kingler used Crabhammer first. An energy sphere was sent across the arena causing whirlpools to form. The attack knocked Poliwhirl into the whirlpools, and another Crabhammer attack knocked Poliwhirl out.
Misty again started with Poliwhirl in the third round against Trinity and her Gyarados. Misty told Poliwhirl to use Bubble, but Trinity responded with Gyarados's Hyper Beam. Gyarados quickly charged up and fired the Hyper Beam, knocking the Bubble away and defeating Poliwhirl.
In Outrageous Fortunes, on the way to Blackthorn City, Misty fought a Trainer with a Poliwrath and lost. Misty started to consider evolving Poliwhirl. Misty took Poliwhirl to the local Pokémon Center to be healed, with Poliwhirl picking up the King's Rock that Ash had won in a tournament on the way. Misty did not notice this, and simply gave Poliwhirl to Nurse Joy for treatment. Shortly afterward, in a battle against Team Rocket, Misty recovered her Poliwhirl via transfer machine from another Pokémon Center and let it out. It was summoned wearing the King's Rock, surprising Misty when it evolved into Politoed before her eyes. Misty was thrilled with her newly-evolved Pokémon.
As a Poliwag it was very friendly, cheerful, and liked to help people as shown when Misty first caught it in The Stun Spore Detour. After its evolution into a Poliwhirl, Misty began to use it in many of her battles, as it developed more stability on land. Poliwhirl, however, also had a bit of a confidence problem, where it tended to hide behind Misty's legs to avoid confrontation. In Hook, Line, and Stinker, Poliwhirl overcame its fears after Misty's other Pokémon offered their support. In its future battles during the Whirl Cup and against Delaney, Poliwhirl leaped into the rounds with visible determination.
After evolving into Politoed, it became particularly cheerful. Its habit of clapping, even at inappropriate moments or when being scolded, often irritated Misty. Though its excellent rhythm proved useful in I Politoed Ya So!, where it took up cheerleading with Tammy's Pokémon cheer squad. Tammy rekindled her interests in entertaining audiences with her cheers rather than winning tournaments, while her own Politoed nicknamed Bean learned Misty's Politoed's clap routine.
Politoed was featured in the TCG as one of Misty's Pokémon. The following is a list of cards named Misty's Poliwag, Poliwhirl, and Politoed.
Misty's Poliwag Cards listed with a blue background are only legal to use in the current Expanded format. Cards listed with a silver background are legal to use in both the current Standard and Expanded formats.