Politoed first appeared as a Poliwag in Murkrow Row, as one of the family Pokémon at Gold's home that he grew up with. When the Team Rocket grunts stole Gold's backpack, containing the Poké Balls of his family Pokémon, Polibo's Poké Ball was washed away by the stream and ended up with a wild Granbull. In Teddiursa's Picnic, Gold found and defeated the Granbull and regained Polibo.
In You Ain't Nothin' but a Houndour, Gold had his first encounter with the Masked Man. His attempts to avoid him were ruined by Polibo being curious about his Gastly, resulting in Gold fighting him. Soon after the fight started Polibo was hit by Gastly's Shadow Ball, forcing Gold to run and hide.
In Gligar Glide, Polibo was seen training inside the Pokémon Day Care, defeating a Donphan. While he was there he saw a commemoration picture of Red's party after his victory over the Indigo League, he had hopes to evolving into a Poliwrath, just like how Poli turned out. After the training was over the Day Care Lady gave Gold and Polibo a King's Rock as a gift.
In Ampharos Amore, Gold and Silver become trapped under the collapsed Tin Tower. Silver tells Gold to send out his Water-type Pokémon, because water will pull up underground water, which will let them escape. Gold sends out Polibo but the maximum amount of water that Polibo can use is too small. Polibo then evolves into Poliwhirl and Silver tells Gold to trade using the Pokédex. Gold does so just as the tower is completely filled with mud. Then, water shoots out of the tower, along with Silver, Gold, Croconaw, and Gold's evolved Politoed. After they escape Team Rocket appears and attacks the group. After a brief fight Gold tells Polibo to use Water Gun, but Polibo ignores him. Silver takes over and commands Polibo to attack their Piloswine, and with the power of liquefaction and Polibo's Whirlpool, Piloswine is defeated.
In Tyranitar War Polibo is sent out to battle against Silver's Tyranitar, and attempts to attack with his advantageous water attacks, but is thwarted by Murkrow and is beaten. Polibo is later used in Delibird Delivery - 1 to battle against the Masked Man again. Gold has Polibo use Dynamic Punch, but Polibo's hand becomes frozen.
In Slick Slowking, Polibo is used to battle against Sham and Carl. Polibo attacks with Hypnosis and manages to put his opponents to sleep, but is stopped when their Magcargo and Slowking continue to attack through Snore and Sleep Talk. Magcargo attacks with a powerful Fire attack and overwhelms Polibo, forcing Gold to recall him.
In The Last Battle VI, Polibo is used in Gold's last battle against the Masked Man. Knowing that Delibird was key to the Masked Man's strategy he had Polibo defeat it with a Perish Song, though this also took him out of the fight.
In The Final Battle VIII, Polibo joined forces with Red's Poli while battling against Guile Hideout. After saving Emerald and his Dusclops from Jirachi's Doom Desire attack, Poli used Double Team to confuse Guile Hideout so that Polibo could get a chance to sneak closer and attack. Although Guile Hideout tried to send his Walrein and Masquerain to attack the Tadpole and Frog Pokémon, they simply threw them away and attacked Guile Hideout directly, breaking his armor.
In Out-Odding Oddish, Polibo is used in the Pokéathlon alongside Aibo and Exbo. They start with the Skill Course, which ends with the round Snow Throw. The team throws snowballs at their opponents, but Gold commands Aibo to create a gigantic one. Aibo throws it, giving Gold enough points to win the Skill Course. The same three are later entered into the Stamina Course and manage to win that one as well. In the next chapter the three enter the Power Course and go up against Koga, Bruno, and Will, members of the Elite Four. When the match starts Gold is shocked to see his team being defeated by his opponents. At Circle Push, Koga's Muk easily pushes Polibo, Aibo, and Exbo away from it. In Goal Roll, Will's Exeggutor kicks several balls into a goal while Polibo, Aibo, and Exbo fail to block them. In Block Smash, Gold faces Bruno and his Machamp as his final opponents. Machamp does a powerful blow that destroys a whole row of blocks instantly while on Gold's side, Aibo attacks the cracked area in the center, but doesn't do much to the block. He switches to Polibo, but he only manages to destroy one. Gold switches to Exbo next, who manages to break more blocks and is the closest to matching Machamp, but not by much. Gold soon reveals that Aibo is attacking for critical hits on the blocks. By doing so, it sends Gold's team into High Tension mode, allowing him to quickly catch up with Bruno. Bruno tries to fight back, but Machamp's arms have become too injured to be used again. Gold has Aibo leap into the air and send a powerful strike in the dead center of the block, destroying them all and giving Gold the win.
In All About Arceus VIII, Polibo is used to fight against Arceus. He attacks with a powerful Bounce, but fails to do any real damage.