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to debug opencv progs using mingw / gdb, you have to:

• build the opencv libs in the DEBUG version (that's a whole seperate cmake && make && make install pass)
• build your prog with -g flag, and link it against the debug libs (-lopencv_core320d , etc)

but the error is comimg from opencv_ffmpeg_64.dll, which was built on another machine, and downloaded to yours as a binary (long story about evading gpl behind that), so the build paths won't match yours ever.