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There are a couple pokemon I'd consider unexpected bros but there is one that stands out as the odd ball.
Wanted an Electric type for my first playthrough of pokemon Ruby; little did I know, Hoenn has nothing but awful Electric types. Luckily, I happened to come across a Minun just north of Staleport; it was obviously a cheap Pikachu clone but it was blue so I kinda liked it. Boy oh boy was Minun a surprise, helped nicely with a Flying and Water gyms. My Minun was Glacia's worst nightmare. I gave it a pro moveset too: spark, shock wave, thunderbolt and Thunder. You might think that wouldn't have worked well at all but my Minun won all the Cool Contests like they were a breeze. Total bro, I miss that guy; wish I knew where he ended up.