The vacancy will be filled by Moya Greene, who takes up the post in July. She is currently the president and chief executive of Canada Post Corporation (CPC).
Donald Brydon, Royal Mail's chairman, said: "She will bring energy, clear thinking and a proven leadership track record – as well as hugely relevant experience – to the business at an important moment in its evolution."
Greene has been chief of CPC since 2005. Before that, she held senior roles at companies including Bombardier and TD Bank.
Earlier this month, the new government's business secretary, Vince Cable, announced .
The same day, Royal Mail announced it had increased its operating profit by £83m in the past financial year to £404m, an uplift of 26%.
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