A former chief executive of the Guide Dogs for the Blind Association, Peacock joined the Charity Commission last July. She began her career in social work and lecturing, and became chief executive of the National Autistic Society in 1989 before taking the position at Guide Dogs.

Her appointment follows the recommendation in the Strategy Unit report for the office of Chief Charity Commissioner to be split between a part time chair and a full time chief executive.

Mr Blunkett said: "Geraldine Peacock has a real understanding of the voluntary sector, as well as of Government. She is the right person to take the Charity Commission forward as a modern regulator, and to develop the complementary role the Commission can play in supporting the voluntary sector.

"She will have a central role in maintaining and building public confidence in charities, so that more people are motivated to give their time, money and talents to the voluntary sector."

Charities Minister Fiona Mactaggart described her as a "tireless ambassador" for the voluntary sector. "Her experience from the sharp end will prove invaluable," said the Minister. "I know she will stand up for the voluntary sector in Whitehall and beyond."

Peacock said: "I relish this opportunity to develop the Commission's role as a pro-active champion of an increasingly diverse sector. I want us to deliver regulation which enables - where charities have responsibility for themselves, and demonstrate full accountability."