In this tutorial, you'll take the picture from this to this:
Open the picture you want to work with. If you want it icon sized, it should be 100 by 100 pixels. :]
I'm using a picture of leaves.
Press control + u to bring up the Hue/Saturation window. Bring the saturation ALL the way to the left so your picture is completely grayscale. Press ok.
Make a new layer. Choosing a large-ish, soft brush, pick a color and click a single time on the canvas. Choose one or two other colors and repeat (don't have too many spots, though!). Change the blending style of the layer to Overlay.
Walah- a purty icon in three easy steps!
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