http://www.skype.com/help/guides/soundsetup_xp.html

Note: I have a SB Audigy card, and one of the options in the "Recording" section of the sound properties (see link above for how to get to that) is one called "What U Hear". When that is selected --instead of the Mic-- everything sound-related that the PC makes will come through Recording output, and that's the output that would feed Skype.

So, look at the instructions in the link above, and make sure that:

A: Mic is muted in the PLAYBACK properties

and

B: Mic is the ONLY thing selected in the RECORD properties (without the mic "boost", too).