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Pretty sure I used it on my old laptop, and it had XP. All the versions should work for XP and up.
Exactly how does it not work? Can it install? Does it open, but throw errors all the time? Does it show briefly in the task manager and then disappear from the list? Does it open but does not connect to the game? Something else?
And have you downloaded the extra files you need for it to run? You can find them here (it's the "Needed Software to run SimPE")
http://sims.ambertation.de/en/download/realdownload/
For the game, are you using the Ultimate collection, or regular game CDs? If you're using the UC, you'll need to do some fixes for
SimPE to recognize your game.