Do you have any 3rd-party apps installed (see under File|Options|Addins)? If so try starting Word in safe mode (hold down the Ctrl key whilst starting Word) and testing whether the mailmerge works there.
I also note from your profile that you're running Word in 64-bit mode. FWIW, MS recommends against this unless you really need 64-bit mode for Excel, the reason being that many 3rd-party apps designed to work with Office are not fully 64-bit compatible and are liable to cause crashes.
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Cheers,
Paul Edstein
[Fmr MS MVP - Word]
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