What a stupid tool! Ctr+G does not grab anything, and the only way to "grab" the right color is to write it down while staying selected.
Thank you, I am back to PS.
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It works for me, probable you dont see the message who says SELECT THE COLORPIC WINDOW TO START GRABBING COLORS" then you press ctrl + g

I had that same problem on Windows 8.1 update 1. Ctrl G did nothing. I closed ColorPic and right clicked on its icon and choose run as administrator. That fixed the problem. You can also right click on the icon and choose properties then choose the compatibility tab and check the box next to run this program as administrator and the hit OK. Now it will always run as administrator.

For those of u who say it doesn't work, how are you using the application?

I tried and tried and i'm one not to give up..so i even tried the portable and the install versions...still nothing...i even uninstalled but liked it so much i had to try again and i found this link that might help you...(http://colorpic.software.informer.com/4.1/) click on video....

First click on the little boxes on top of ur color pic and then hover ur mouse over the color u want...then hit ur control + G key, it will say grab color...and so on for the next color...always click on a little box on top to start the capture...It workssssssssss!!!!!!!!!