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>Espeon
Eevee has always been one of my favorite pokemon of all time, and the same goes for its evolutions; Espeon just oozes class and sophistication and hits like a juggernaut. Collosseum was also really fun when I was a kid.
>Flygon
On my first run through Sapphire, I caught a Trapinch, not knowing what to expect, and lo and behold, when that nigga evolved, shit got real. Designwise, I like how sleek Flygon is, and in terms of competitive play, it plays more like a precision weapon than a nuclear bomb, due to his 100 base atk. Unfortunately, I think the power creep is gonna knock him out of UU for Gen VI, but he's still a favorite.
>Umbreon
Much like Espeon, Umbreon was a bro in part due to Collesseum. When I was like 7ish, I learned that Eevee could evolve via high friendship into Espeon, so I tried to get one as hard as I could. While I was grinding with it, the clock rolled over into night mid-battle and my Eevee evolved into an Umbreon. I was initially disappointed with it, especially since I could not get him to kill anything no matter how hard I tried. Then I realized he never died. Then he got Moonlight, and REALLY never died.
>Volcarona
When BW first came out, I read up on Volcarona, and loved everything about it. Design, stats, movepool, competitive viability. It was all so sick. I thoroughly enjoyed the Bug/Fire combination, and moreover the fact that it can still exist in OU despite a 4x weakness to Discrete Gravel just because of the raw power it packs in sun. Hell, the fact that it works in rain with a bulky Hurricane set makes it really interesting.