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You can't catch Shaymin in sky form, but you can find the land form and then change it. You can find Shaymin in land form in Flower Paradise in Sinnoh. Flower Paradise is an event-only area and you'll need Oak's letter (which is an event item). After you've caught Shaymin in land form, you need to visit the Flower Shop in Floaroma Town. A blonde woman near the Flower Shop will give you the Gracidea Flower. If you give this to your Shaymin, it will transform to sky form. However, it can't stay in sky form during the night, when he's in a PC or when he's frozen.

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