from what i see, it's just a universal remote, you will need a receiver for the actual pc. universal remote's are almost always programmable, so im sure you could get it to work if you could find a receiver that works with both mce and the remote.
Holy crap!!! That's a sweet looking remote...apparently a little fiddly to get used to, but sexy as :worship: . I've looked at some reviews for it, and couldn't find out whether it was compatable with XP MCE 2005, but as nabberuk said "it's a universal remote, it should be able to be programmed for it"