Thorpe will join in September following more than eight years at HSBC, where he was most recently head of personal finance media relations.
In the role, handled internally since the resignation of Henderson at the start of the year, he will report to Mastercard's European group head of comms Rose Beaumont.
Beaumont said: "The UK continues to be a huge priority market for Mastercard and a very exciting space for our comms. James brings expertise and talent that really adds to our stellar team."
Thorpe joined HSBC from Egg, where he was head of personal finance PR, and before that was PR manager at Consolidated Communications.