I recently had to (remotely) debug an issue on windows involving PostgreSQL and PL/Python. Basically, two very similar computers, with Python2.5 installed via python(x,y), PostgreSQL 8.3.8 installed via the binary installer. On the first machine create language plpythonu; worked like a charm, and on the other one, it failed with C:\\Program Files\\Postgresql\\8.3\\plpython.dll: specified module could not be found. This is caused by the dynamic linker not finding some DLL. Using Depends.exe showed that plpython.dll looks for python25.dll (the one it was built against in the 8.3.8 installer), but that the DLL was there.
I'll save the various things we tried and jump directly to the solution. After much head scratching, it turned out that the first computer had TortoiseHg installed. This caused C:\\Program Files\\TortoiseHg to be included in the System PATH environment variable, and that directory contains python25.dll. On the other hand C:\\Python25 was in the user's PATH environment variable on both computers. As the database Windows service runs using a dedicated local account (typically with login postgres), it would not have C:\\Python25 in its PATH, but if TortoiseHg was there, it would find the DLL in some other directory. So the solution was to add C:\\Python25 to the system PATH.