Since sound works everywhere else properly, it is probably a setting within Skype that needs to be changed. These aren't specific to Windows 8.1, but it might give you an idea of what to look for:
How do I configure Skype to work with a new headset, microphone or speakers?
How do I use my USB phone or headset for Skype calls and my loudspeakers for all other audio in Skype for Windows desktop?
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Re: windows 8.1 skype no sound thru headpnones
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