Setting "Verify" to false just turns off the certificate check so that any old certificate is accepted without error. This is of course a security risk and should never be used outside of development.
IIRC. The LabVIEW HTTP functions use cURL and the "ca-bundle.crt" located in \National Instruments\Shared\nicurl. It contains the certificates of the Authorities. Adding the servers' certificate or the servers' trusted root certificate to that list once you have ascertained the certificate is correct for that website; is the recommended procedure for adding ad-hoc certificates (thus keeping "Verify" = True).