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Goldeen was first used in Pokémon Emergency! to distract Team Rocket whilst Ash rescued the Pokémon in the Pokémon Center. Its "battling" consisted of flailing around on the floor. Misty quickly recalled it.
Goldeen has proved helpful when Misty and her friends need assistance swimming or locating something underwater. In Pokémon Shipwreck, Goldeen tried to find an exit out of the sunken S.S. Anne. Instead, it discovered Team Rocket, who would otherwise have drowned. Goldeen then swam to the surface with her Trainer, whilst Starmie and Squirtle followed behind with Ash and Brock. It was later sent out to attempt to drag the raft away from James's Gyarados, but they were all caught up in the Dragon Rage and sent flying. She reappeared in Tentacool & Tentacruel, where she helped Staryu and Starmie rescue sailors who had been attacked.
Misty does not use it very often because it cannot battle or maneuver outside of water. When it was, it often did poorly due to its lack of battle experience. An example of this is a battle against Marina in Bye Bye Psyduck, where it lost to her Tentacruel, before Misty's Staryu took over and won.
Orange Islands
Goldeen was sent it out in an attempt to fight a wild Snorlax, but it was completely helpless and was almost eaten before being recalled.
It was also used against Molly Hale's Kingdra in Spell of the Unown, where it was swiftly defeated. It was again succeeded in battle by Staryu, presenting a potential hierarchy structure within Misty's team, with Goldeen being the apparent weakest.
Goldeen using its tail as a rotating shield to deflect Qwilfish's Pin Missile
It fought Dorian's Qwilfish in Just Add Water, managing to land a Horn Attack after dodging Qwilfish's Tackles with Agility. Goldeen then used Supersonic, but Qwilfish shrugged off its effects and fired Pin Missile. Goldeen managed to reflect those coming its way by spinning its tail. Goldeen aimed a Horn Drill, which Qwilfish dodged. Qwilfish used another Pin Missile, hammering Goldeen from behind. A final Take Down was enough to knock Goldeen out and win the round for Dorian.
A † shows that the move was used recently, unless all moves fit this case or there are fewer than five known moves.
In the manga
In the Pokémon Adventures manga
Misty's Goldeen in Pokémon Adventures
Misty's Goldeen makes a brief appearance in the Pokémon Adventures manga. Misty used it in her battle against the Ghost Pokémon of Agatha that were attacking Cerulean City.
Despite debuting in the second episode, Pokémon Emergency, Goldeen did not actually use an attack until Bye Bye Psyduck, 89 episodes later.
Goldeen holds the record for being absent for the most episodes while being in the party of a main character, 34, not appearing after Tentacool & Tentacruel and before The Purr-fect Hero.
Despite being infamous for being all but useless on land, in the Pikachu shortPikachu & Pichu, Misty's Goldeen is seen being able to hop around on land to move.
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For more information on this Pokémon's species, see Goldeen.