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Other than Sylveon, of course, because it only has one in Valerie (I think).

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excuse me you have forgotten the best one serena
Do you mean in the anime or games or both? Either way, what would you use this information for?
You answered your own question. It's sylveon
Why this downvoted it’s got nothing wrong with it.
I’m using it for a character I’m making and I want them to have the least used Eeveelution. For uniqueness.
Anime or games or both?
Probably both
If you want uniqueness why don't you want Sylveon then?

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Best answer

Sylveon has the least notable trainers that use it (anime & games). Espeon is 2nd (for least notable trainers).

Source: Bulbapedia (Pokémon pages) & Serebii (Trainer Pokédex pages)

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