This article from Adobe's "Create" magazine is a great peek into one artist's method of creating her artwork. The seven videos show how the artwork evolves to the finished image and really showcase how to use tools in Photoshop, to create your own personal vision.
Check it out here:
When Photoshop Is Your Paint and Paintbrush | Create
If you have not had a chance to paint in Photoshop, this article provides a great starting point with which to begin.
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