Kolkata-born Millie Banerjee will oversee the professional body for everyone in policing and make sure officers and staff have the skills and knowledge they need.
"We are dedicated to providing access to the best knowledge and skills which sits behind the bravery, dedication and compassion shown by police on a daily basis. We have ambitious plans ahead and I intend on working with people across policing to continue building a professional body that supports all officers and staff," Ms Banerjee, 71, said.
The UK government said her appointment alongside the newly-confirmed Chief Executive of the organisation, Mike Cunningham, will help professionalise policing.
"Working with Millie over the last year I have been impressed by the insight she brings from her time leading other public and commercial organisations, including the British Transport Police, said UK home secretary Amber Rudd.
Ms Banerjee, honoured with a CBE by Queen Elizabeth II in 2002 for her work in supporting civil service reform, has had a long and varied career in the private and public sectors in the UK.
She was the Chair of the British Transport Police Authority for seven years and held several non-executive appointments, including as non-executive director of the UK Cabinet Office, the Prisons Board, the Peabody Trust and media watchdog Ofcom.
She is currently the chair of NHS Blood and Transplant and a board member of East London NHS Foundation Trust.
Rachel Tuffin, interim CEO at the College of Policing said: Millie brings a wealth of experience from the private and public sectors, including several years in policing.
Having spent years in policing, Ms Banerjee said in her role she will work to help staff tackle "ever more complex crime" amid a reduced workforce and greater demand.
The College of Policing, established in 2012, is a not-for-profit membership organisation with a remit to provide those working in policing in England and Wales with the skills and knowledge necessary to prevent crime, protect the public, and secure public trust.