I have used Pixie for years and years, and use it daily...
If you are serious about your themes, and css in general it can come in bloody handy !
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i am more into kuler.
I hate flash and adobe though. Apart from Photoshop . Pixie is very cool.. all of our guys use it
if it was about what we use... i'd just take a RAL color catalogue and write #numbers on it
Gimp has a feature like this (picking colours from anywhere on the screen) build in:
I use the default one in fireworks