I agree with Richandhazel that it could be anything, but depending on how bad the problem is and how much time you have, check the water pump.
We had an overheating problem once. The VW dealership had no idea what it was - but they said they'd replace the engine for 1500 quid, which was nice.
However, our local mechanic discovered that the water pump was the culprit. It had shed all its blades and the water was going nowhere.
Regards,
Justin