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Rayquaza first appears in "Destiny Deoxys" and I believe it is captured in the Ninth Pokemon movie.

If you wish to capture it, it can only be found in the sky pillar in Pokemon Ruby, Sapphire, and Emerald.

Fore more info, please visit this link to the Pokemon wikipedia: http://bulbapedia.bulbagarden.net/wiki/Rayquaza_(Pokemon)

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