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I'm just getting started in linked battles in 3rd gen.
So...
If I want to use this Charizard: - Belly Drum/Earthquake/Substitute/Fire Blast
What's the better nature? Adamant or Naughty? Is it irrelevant if I use the correct EV's??
Naughty would be best if you do decide to use Fire Blast, but it's generally better to go with HP Flying or Aerial Ace to benefit from Belly Drum more.
For EVs...
With Fire Blast: 252 Atk / 4 SpA / 252 Spe
Without: 4 HP / 252 Atk / 252 Spe