Rhodes replaces Tom Hings, who left the postal operator earlier this year without a job to go to.
The payment services company confirmed his departure and said it would replace Rhodes “in due course”.
Rhodes has been in his current role at the payment services provider for almost five years. Prior to Mastercard, he had stints with McCann Erickson as an account director and Bilsland, Coltmann McKenna as an account manager.
Royal Mail’s commercial and marketing departments restructured two years ago to facilitate a more “customer-led” business and marketing approach.
As part of the overhaul, Luisa Fulci was promoted to director of marketing services, leading a team that included Hings, and Mark Thomson, who was appointed media director.
MasterCard appointed former John Lewis marketing director Gill Barr to head up marketing for the UK and Ireland in March. Its Worldwide business appointed Alfredo Gangotena as its chief marketing officer in April.