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How do you get XP Home to recognize and respect each user's choice of default programs?
I guess we can only hope that one day Microsoft will come up with a real multi-user OS and finally become as usable as Linux. ;)
Assuming that both users actually log out and log in (rather than user fast switching) you could use a .reg file for each user to change the system-wide default at log-in. It's a dirty hack, but without using additional software, that's probably the only way to do it.
Personally, I would ask the IE user why they don't like Firefox and then try to change his/her mind.