Yes it can. It won't automatically add the music though.
Essentially all iTunes is, is a music organiser, combined with an online store and a simple way to get the music onto the iPod.
You can't use the online store (though I'd suggest never using that anyway, even with an iPod), and you'll need to find your music in "c:\documents and settings\[username]\my documents\my music\itunes\itunes music", and then copy the files across you want onto your generic mp3 player.