Answer 1

In the episode 'May's Egg-Cellent Adventure' Pikachu is going to stop team rocket with a Thunderbolt but he is told to stop part way through charging. Later Ash tells him to use quick attack and Pikachu, charged with electricity, does a Volt Tackle instead.

Sources: http://bulbapedia.bulbagarden.net/wiki/AG150

Comments

Nice answer

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Thanks!

Answer 2

If I remember correctly It learned it in the Hoehn Region.Ash and Pikachu did some Special Training working on that move.After some practice Pikachu Mastered it and became a legend :P

Comments

What do you mean became a legend?

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I mean he became so powerfull that he's almost a legend.He has acomplished a lot of things with Volt Tackle