Yes, I see tivolibre.exe (version 0.7.4.0) in the BIN folder. I'm running Windows Defender, no other antivirus software.Looking at the code. That exact error means it's having trouble opening tivolibre for decoding.
In the pyTivo install folder, under bin, do you see tivolibre.exe?
Could your antivirus software be blocking it for some reason?