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Articuno in Pokémon Blue. It is the first one you meet. (Although, if some people couldn't move the rocks correctly, then, probably it was Moltres the first one they met.)
I think it was Moltres. I can remember I used all my Poke/Great/Ultra-balls on it, and I was like: Lets try this one! *Throws Masterball* Ding! WHOO! I GOT IT! Lucky me : DD
The happiness of a n00b ... lul