Misty rarely used Starmie in battle, generally favoring Staryu to battle on land and often Psyduck by mistake. Starmie was typically featured in a more instrumental capacity than its pre-evolved counterpart, being used to traverse water on many occasions.
In The School of Hard Knocks, Misty was incensed by Joe's insistence that he could easily defeat her Water Pokémon as he had done it countless times on the simulator. She promptly challenged him to a real battle, and sent out Starmie to prove its strength against his Weepinbell. Starmie used a single Water Gun and knocked out Weepinbell, leading to Joe's ridicule by Giselle. However, Misty then challenged Giselle, calling her out for not being a true friend. Giselle's Graveler proved to be a very powerful opponent, deflecting Water Gun by spinning and then smashing into Starmie, shattering the center gem and knocking it through the window and into the pool. Starmie's regenerative abilities were also demonstrated, as by the next time it was seen, its central core was repaired.
It appeared to have an Ability similar to Water Absorb, even though Abilities did not exist when Misty was a main character. This was demonstrated when, in Bye Bye Butterfree!, Starmie chased Team Rocket away with a Tackle, but was knocked out when Jessie smashed it with a hammer. However it seemed to regain its health when Misty jetted water on it. In Pokémon Scent-sation!, it helped Staryu and Squirtle put out the fire at Celadon Gym with Water Gun.
Starmie paired with Misty in The Flame Pokémon-athon!. It made the final four as it was able to surf across the river course. However, like the other contestants, it's efforts were sabotaged by Team Rocket and it was blinded by a Sludge attack from Weezing, taking it out long enough to allow Dario, the man who had encouraged Team Rocket, to make a break for the finish line.
Misty attempted to round off her team of four in Princess vs. Princess with Starmie, but Psyduck popped out of its Poké Ball instead. This happened quite commonly with Starmie and Psyduck.
In The Misty Mermaid, Misty stopped off at the Cerulean Gym after Horsea was feeling sick due to a lack of open water exercise. Misty also left Starmie there because her sisters wanted to borrow it for their water ballet performances.
As Starmie wasn't given very many onscreen appearances, little is known about its personality. When in battle, it was shown to be quite obedient and loyal to Misty. Starmie has been known to sometimes droop and bend its points when in pain or disappointment.
In her Sync Pair Story "A Day with Misty", Misty explains that the Starmie she uses in Pokémon Masters is not the same Starmie she uses in her Gym battles. This Starmie hatched from an Egg found at the Pokémon Day Care after Misty left her Gym Starmie there.
Starmie was used during a Gym battle against Red in Suddenly Starmie. The challenge didn't last long, however, as Starmie easily defeated Saur after a failed Vine Whip did little damage. However, she stated it wasn't strong enough in Mt. Moon to battle Koga's Rhydon. The battle between Bulbasaur and Starmie was merely a demonstration for Misty to show how ill-prepared Red was for facing the dangers that undoubtedly awaited them. She ended up giving him the Cascade Badge after a few days of training together. In You Know...Articuno!, Starmie was shown floating Misty around after when she traded her Gyarados away to Red for him to surf with.
In Lovely Lanturn, Starmie used its psychic powers to write out Suicune's thoughts, telling her about the dangers of the Masked Man. Starmie was later seen defeating Mil Mil with a quick succession of attacks in the Gym Leaders' exhibition match.
It was last seen fighting against mind-controlled Team Rocket Grunts.
Related cards 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.