This was happening to me a lot before and running Windows updates seems to have resolved those problems. However, this was over a year ago when SharePoint 2010 was first rolled out. More recently, more and more people were calling with this problem and I wasn't really coming up with a solution.
Hey presto. It seems to be that Open with Explorer does not work with IE 64 bit. So get your user to switch back to 32 bit and it should work fine.
We recently rolled out 64 bit machines across the company, hence the increase in this problem.
:)
Thanks for sharing... that just saved me time trying to answer one of our customer questions that came in on a help desk case. :)
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