Peter Knott joins the new Government-funded bank after a career which has included jobs at some of the industry's biggest names.
Mr Knott was chief financial officer for JPMorgan Chase's New York-based global investment banking coverage and mergers and acquisitions groups before moving to Standard Chartered, where he held senior roles including group head of operational risk.
Mr Knott will be based in the Green Investment Bank's Edinburgh office.
The bank's chief executive Shaun Kingsbury said Mr Knott would bring a wealth of relevant experience. The bank will be able to draw on £3 billion Government funding to encourage private sector investment in the green economy.
Mr Knott said: "I am very excited by this opportunity to join the bank at this early stage in its development as a leading institution in the financing of the UK's renewable energy sector."
Last month, the Green Investment Bank appointed Rob Cormie, the former Quayle Munro executive, to the key role of group operations director in Edinburgh.