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who is better?

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In honesty, because it's for an in-game team, just pick whichever you like best.

However, looking at things objectively, Starmie is the far superior option.
Here's why:

  1. Dual type makes it much better when it comes to covering for your other team members. as well as being able to use 2 STAB moves.

  2. Better stats. Starmie has high Speed and Special attack, so it is used as a sweeper. Vaporeon has a high HP, yet a low defence and a mono type water which doesn't have many resistances and not very many stall/healing/status moves.

  3. Starmie can be taught an multitude of effective moves such as Psychic, Thunderbolt, Ice Beam, and Surf. Vaporeon however, learns its first effective water type move at level 51 which is Hydro Pump (or Surf via hm), and other than being able to learn Shdow Ball and Ice Beam via TM, it doesnt have any intersting moves that it can learn.

BUT like I said If you prefer Vaporeon, by all means use it. Ingame isn't much of a challenge if you know what you're doing and you should just try to have fun with it.

edited by
Can't Vaporeon also learn surf pretty early?
Still doesnt make Vaporeon any better.
You get Eevee a fair bit earlier than you get a Super Rod so I'd say Vaporeon should at least get a bit more credit since its stats are fairly high compared to the other obtainable Water types. You can always just hold on to the Water Pulse TM from Misty until you evolve Eevee. On top of this, it also gets Bite and Aurora Beam fairly soon after you get it for some nice coverage. Of course, statwise Starmie is the infinitely superior option by virtue of stats and movepool alone, but for anyone interested in using an Eevee I'd debate Vaporeon to be one of the better choices.

Also Shadow Ball is garbage on Vaporeon because it's physical in this generation. Yeah, I'm not arguing how atrocious its TM learnset is.