In some older versions of Word, you could pick printer in Word and click a "make default" box; and it would apply to all Office programs. That option seems to have gone away in XP, in favor of the somewhat simpler setup via Start - Settings - Printers. (That's "simpler" as compared to going all the way into Control Panel to get to printers, as you did in some older versions.)

The "new Word" Envelopes and Labels are one of those places where you don't get an option to switch printers, and I suspect that some of the Mail Merge and Form Letter choices may be similar, but I haven't looked. I don't often use the "standard" setup, even for envelopes, because I often like to "add graphics." It could probably be done simply enough in the "canned" methods, but I haven't bothered. Just make a picture and print to "envelope size paper." And I don't send enough mail to need "automation."

John