I had asked on Twitter if there was a shortcut to copy the hex value of a color selected within Photoshop with the eye dropper tool. Sean McCabe replied with the handy tip that you can set a keyboard shortcut to copy a colors hex value. I quickly assigned this to my handy F Keys which I used exclusively for Photoshop shortcuts.
The workflow is as follows: select a color with the eye dropper, switch to Sublime Text and paste into my CSS.
Edit: Dries Delaey also noted that you can simply right click on a color with the Eye Dropper and copy the colors hex value.