One would expect that when the caller explicitly asks to make unverified requests, then the REQUESTS_CA_BUNDLE environment variable doesn't affect it. The reality is different, however.
import os
import requests
os.environ['REQUESTS_CA_BUNDLE'] = 'asd.pem' # Must be an existing file
r = requests.get('https://self-signed.badssl.com/', verify=False)
print(r)
# Prints: <Response [200]>
session = requests.Session()
session.verify = False
r = session.get('https://self-signed.badssl.com/')
print(r)
# Fails: requests.exceptions.SSLError: [SSL: CERTIFICATE_VERIFY_FAILED] certificate verify failed (_ssl.c:749)