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Episode 105, Charizard Chills

Charizard gets frozen by a Poliwrath and learns to trust and obey Ash when he takes care of Charizard until it recovers.

Source: Bulbapedia (and I remember it from watching the anime)

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Oh, so that's the Orange Islands series. I guess Ash couldn't train him during the Indigo League series...
I admit that I never got to watch consistently, but I always thought it was after the Charizard ranch episode...