His appointment comes as the fledgling organisation has been handed a pound;400,000 in development cash by the Sector Skills Development Agency.
Ministers say the development stage should be finished in June, after which the organisation can be given a licence to operate.
Mr Hedger was formerly at the Department for Education and Skills as deputy secretary for schools and, latterly, operations director responsible for training and enterprise councils and national training organisations. He said: "It's three years since I was at the DfES and I believe I am capable of an independent view balancing the various interests.
"I think the timescale we have been given is challenging but I can understand why ministers want to see this up and running as soon as possible."
The SSDA is overseeing the creation of SSCs across the range of industry sectors. Between 20 and 30 will be created, replacing the the network of 72 national training organisations.
As well as agreeing training standards for post-16 education, the SSCs will act as the employers' voice in vocational training.
David Hunter, chief executive of the Further Education National Training Organisation, one of the partners of the new SSC, said: "It was important we got someone of the right stature and who is from the lifelong learning sector to be chairman.
"This is an interim appointment. I hope that the different interests within the SSC will be in a position to appoint a chairman from among the post-16 education employers by the time the SSC gets its licence to operate."
FENTO's partners in the SSC are the Higher Education Staff Development Agency, the Employment national training organisation and Paulo, representing youth and community work.