Ms Rose, currently deputy CEO NatWest Holdings and CEO commercial and private banking, will take up the position on 1 November after an “orderly handover” has taken place.
Ross McEwan will formally step down as CEO on 31 October 2019.
Ms Rose will also be appointed as executive director and CEO on the boards of NatWest Holdings Limited, The Royal Bank of Scotland plc, National Westminster Bank Plc and Ulster Bank Limited.
RBS chairman Howard Davies said: “I am delighted that we have appointed Alison as our new CEO.
“She brings extensive experience and a track record of success from her previous roles at the bank.
“Following a rigorous internal and external process, I am confident that we have appointed the best person for the job. “I’d like to take this opportunity to thank Ross, on behalf of the board, for his leadership and commitment during his time as CEO and wish him the very best for the future.
“Ross leaves a strong platform for his successor; a bank that has refocussed on its core markets in the UK and Ireland and resolved all its major legacy issues, while returning to profitability and paying dividends.” Alison Rose said:
“It is a huge honour to have been appointed as the new CEO of RBS and I am looking forward to getting started.
“As one of the oldest and most important financial institutions in the UK, we have a key role to play in supporting the economy and championing the potential that exists across the country.
“Under Ross’ leadership, RBS has undergone a significant transformation and, as part of his leadership team, I am extremely proud of all we have accomplished and I would like to thank him for the support he has given me over the last six years.
“Maintaining the safety and soundness of this bank will continue to underpin everything we do, as will our commitment to our customers and to delivering steady returns for our shareholders. “This is an exciting time as we enter a new chapter for this bank.
“Our industry is facing a series of challenges; from the ongoing economic and political uncertainty to shifts in the behaviour and expectations of our customers, driven by rapid advances in technology. “It will be my priority to make sure we are ready to meet these challenges and build the best bank for families, businesses and communities.
“We will be driven with real purpose in our work to help achieve the goals and potential of our customers and be there for them at key moments in their lives.” Ms Rose is also a non-executive director of Great Portland Estates and sits on the board of the Coutts Charitable Foundation.