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My first Level 100 was either the Aerodactyl you get via trade in Gold or my Meganium in the same game. Can't remember which happened first-probably Aero.
Meganium from Gold Version. Man, I was ecstatic when I got it up to Level 100. Too bad my game was erased... I don't know how it was, but it was. It can still save.
Glalie on Pokemon Ruby. My first ever game was Ruby. As soon as I discovered a Snorunt, I got addicted to training it, and after about a week or so I had a Glalie, Level 100.
The first one I got to 100 was a Mewtwo on Silver. I had the boosted experience from trading it from my Blue, or else I wouldn't have had the patience.