ImportError: DLL load failed: %1 is not a valid Win32 application
The ImportError message is a bit misleading because of the reference to Win32, whereas the problem was simply the opencv DLLs were not found.
This problem was solved by adding the path the opencv binaries to the Windows PATH environment variable (as an example, on my computer this path is : C:\opencv\build\bin\Release).
You could try installing the 32 bit version of opencv
I just hit this and the problem was that the package had at one point been installed in the per-user packages directory. (On Windows.) aka %AppData%\Python. So Python was looking there first, finding an old 32-bit version of the .pyd file, and failing with the listed error. Unfortunately pip uninstall by itself wasn't enough to clean this, and at this time pip 10.0.1 doesn't seem to have a --user parameter for uninstall, only for install.
tl;dr Deleting the old .pyd from %AppData%\python\python27\site-packages resolved this problem for me.