Let me just preface with the fact that I used PS CS for this icon. Also, please do not recreate the exact same icon that I'm teaching you how to make unless you then proceed to credit me. If you don't well, then that's just stealing.
First let's work on the background for the image. Fill your 100x100 blank canvas with #D7D7D7. Paste this texture by peoplemachines onto the grey. Set it to soft light.
Alright let's get to the image of Mia Kirshner. It's probably not going to be the exact same thing I did originally (since I forgot how I did it lol), but it'll be close. And I'm not gonna lie, it's gonna take a while.
Duplicate your image and set it to screen at 60% opacity.
New adjustment layer: Curves. Set to soft light.
New adjustment layer: Color Balance. Settings:
+41, -20, +28
-60, +22, -14
+4, -7, -18
New adjustment layer: Hue/Saturation. Settings:
-16, +16, +16
-14, +37, 2
New adjustment layer: Curves.
Create a new layer and fill it with #8FE1FF. Set to color burn.
Create a new layer and fill it with #E4E3E1. Set to color burn.
Crop image to 57(w)x59(h). Paste onto the previously made grey background. We want to sharpen the image of Mia, so go to Filter >> Sharpen >> Unsharp Mask.
Take this texture by tragic_icons and crop it down so that it fits next to your image of Mia.
Create a new layer. Using your eyedropper tool, pick one of the grey colors from the background. Select your 5px blur-brush and, with the grey color, go over the outer edges of both the Mia image and the cropped texture so that you wind up with softer edges.
To finish it up, I used the Daisy Script font on 8pt (available for download at DaFont.com) and typed "black dahlia".