Honestly, I have found that fiddling with Catalyst AI has helped improve performance in some games dramatically, unlike what random said.
For example. When I played America's Army 3 i got very low fps, even with a pretty beefy hardware setup that I have, just changing the Catalyst AI to 'normal' from 'advanced' gives me a huge fps boost.
Another example is when I play Killing Floor, in this scenario I click on the 'disable' catalyst AI box, and it increases my fps by 3 times or more! Going from 30fps to 90 is a big difference.
Another game that seems to use Catalyst AI is Empire Total War, if I change the slider from advanced to normal, I get huge fps losses for some reason, therefore I leave it on advanced.
My last scenario is for old games, for example: Mafia, which I just picked up. Disabling Cat AI give me the steady 60fps that I need, which is the cap.
Now I would theorize that the reason playing with catalyst AI helps me dramatically in these four (but not only) scenarios, is that for one, Killing floor does not support Crossfire to my knowledge, and by disabling AI, it forces the game to use one GPU, which actually dramatically increases fps. Also, America's Army 3 is kind of a buggy game and it takes alot of fiddling to get decent fps. And Mafia is an old game, which we all know sometimes old games need fiddling with just to run. Lastly, I run Empire Total War totally and utterly maxxed out at 1920x1200, which require huge amounts of graphics horsepower, however I can still run it at 60+fps, espescailly with AI on advanced.
Basically, I would say that as a rule of thumb, if a game is performing less than what it should be OR if you are playing a game that is kind of older, play with the catalyst AI settings and see if it helps. It is very easy, in most cases you can just alt+ tab and change your settings, then go back into your game and check to see if your frames are lower, or higher.
Most likely I have a very special situation, seeing as how I have 3x 4870 in crossfire, so obviously if you have one gpu, you may not see the effects that I have just described, good luck!
EDIT: Btw, whenever I can, I just leave it on 'advanced' this seems to be the best options for games in general.