Our internal plumbing is different, so the extension APIs aren't the same, thus PHP extensions can't normally be used with HHVM. Paul has a source-compatability transformer which works for simple extensions (no fancy stuff allowed), but we recommend anyone with an extension consider porting the code.
If your extension is one of those "This was written in PHP but we wanted it to be faster so we turned it into C" types, you should consider going back to PHP for it. In practice, we find that HHVM can JIT PHP code into running about as fast as (sometimes faster than) C/C++ extension code.
If you do need to dip into C/C++ (because you're calling an external library), the API we've designed is a LOT easier to work with than PHP's. And I say that with the authority of having written THE book on writing PHP extensions: http://amazon.com/dp/067232704X .
I'm working on proper documentation for extensions as we speak, but for now you can find some very basic info at https://github.com/facebook/hhvm/wiki/Extension-API .
Get dozens of book recommendations delivered straight to your inbox every Thursday.