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I might get some flak for this...
>Gen 1: Charizard. My very first starter.
>Gen 2: Crobat. That speed and Toxic were extremely useful.
>Gen 3:Gardevoir. Calm Mind before the 7th gym. It swept through Wattson, Flannery, and Wallace/Juan no problem.
>Gen 4: Lucario or Empoleon. The physical/special split and DD boosted Tyranitar to bro tier as well.
>Gen 5: Scrafty genuinely surprised me. But a DD set very quickly proved itself to be insta-bro tier. Though Volcarona gives it some competition.
>Gen 6: Sylveon almost never failed to come through for me, especially with a calm mind set. And, I might get some flak for this, but Pikachu as well. I didn't even plan on it, but it had the perfect nature and a Light Ball when I caught it. With investment in Sp.Atk and Speed, it pretty much laid waste to any water type it encountered. Even Lysandre's Mega Gyarados.