Hi,
check the content types associated with the doc lib, also make sure the template is correct under
doc lib settings > advanced settings > document template
try to delete and add a new word template under forms folder by opening doc lib in explorer view
hope this helps
Warm Regards, Pratik Vyas | SharePoint Consultant | http://sharepointpratik.blogspot.com/ | Posting is provided "AS IS" with no warranties, and confers no rights