I don't know exactly why you're getting that message, but to start from a better baseline, I'd try 2 things:
- Use Python 3.5+
- Make your attempt using the latest requests
If you still get the error, you'll have to debug why it thinks the cert failed and probably view the cert. Is it bad, date, on the CRL, etc.
You could also try with curl to see if it's the cert or Python/Requests itself that is the problem.
curl -kv https://www.cisco.com