Baroness Jill Pitkeathley, the former chair of the New Opportunities Fund, has been appointed chair of the independent advisory board of Futurebuilders.
The board will advise ministers on the objectives, governance and effectiveness of Futurebuilders, which was set up with £125m from the Treasury to fund new ways of delivering public services by charities.
The £400-a-day post requires a commitment of 40 to 45 days a year. A further eight board members will be recruited from the private and voluntary sectors.
Pitkeathley, who is also president of Volunteering England and chair of Cafcass, said: "I have spent most of my working life in or with the voluntary sector. I am strongly committed both to the principles by which the sector operates and to making it as effective and strong as possible. I feel confident and excited about chairing this important group."
Pitkeathley has at times been critical of voluntary organisations in general. In a speech given in the House of Lords last year she accused charities of being reluctant to change and "constantly complaining about how much more money they need".