Is this a pulley on which the the serpentine belt runs? Usually those are kept in tension by one of the accessory pulleys, or a separate pulley. You'll need to start by loosening the tensioner/lightening the tension on the belt, and removing the belt. From there, many pulleys have multiple bolts holding them - you can use one wrench to hold the pulley in place (on a bolt) and another to loosen the bolt.
Be careful, though - depending on which pulley you're removing, and whether or not your engine is an interference engine, you'll want to be careful not to turn the pulley, or you risk damaging the internals (valves or pistons).
Which pulley are you in reference to? Can you get a pic/video of the specific pulley?
Fig. Fig. 12: To remove the serpentine belt from the 3.3L and 3.8L engines, rotate the tensioner assembly clockwise
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