Yes and no... The system that the Canon flashes use is OPTICAL, and the Pocket Wizards are RADIO slaves. They cannot communicate with one another. BUT, you can totally use your 580ex with PWs. You just need to buy two additional cables so that you can hook the PW's up to the hot shoe of the 580ex. From there you just gotta set your flash to manual and find the right settings for the given situation, and you're set. I'm actually running this setup right now and I'm happy with it...
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