I suspect you have the same problem I've run into. If you have a 64-bit version of Python, it cannot load 32-bit DLLs. OpenCV currently only ships 32-bit binaries. If you want 64-bit .pyd and .dll files, you have to compile them yourself. There are some instructions on the OpenCV Wiki, but it's not for the faint of heart. Expect to have a substantial time investment.
The easiest solution is to:
- Uninstall 64-bit Python
- Install a 32-bit distribution.
The PythonXY distribution includes pyopencv -- a good set of OpenCV hooks. The only limitation is that it's 32-bit, so don't make plans to process gigapixel astronomy data with it! ;)
If you must have the 64-bit version, follow these instructions to get it OpenCV to compile with Visual Studio 2010. There's a discussion on stackoverflow that describes building 64-bit apps with VC Express.
EDIT: OpenCV now ships with 64-bit Python binaries. The .dll files need to go somewhere in your path (I put them in the scripts folder), and the .pyd files go in your site-packages directory.