Rhodes, who will assume the boardroom position in April, he is currently director of retail distribution for Alliance and Leicester.
He will pick up the responsibilities of the position vacated by former sales and marketing director John Sutherland, who stepped down in September following Nationwide's decision to bring in a senior marketing specialist at boardroom level.
A Nationwide spokeswoman said the appointment is part of ongoing internal restructure, affecting the sales, product and marketing departments.
The company is still searching for a marketer to replace former head of brand strategy Peter Gandolfi, who departed late last year.
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