The GLC, under Mr Livingstone's leadership, was responsible for education in inner-London until the organisation was abolished by the Thatcher government in 1986.
This time, as Mayor of London, he will chair a new body responsible for the funding of adult education. The vice-chairman of London's new "skills and employment" board is expected to be appointed from the world of business.
Mr Livingstone said: "The skills board provides us with the opportunity to work with business, employers and trainers to ensure all Londoners can contribute to and benefit from London's economic prosperity."
His return comes after the Greater London Authority and the London Development Agency - both of which are under his control as mayor - attempted to wrestle the whole of further education from the Learning and Skills Council.
Both have long argued that London's skills training requirements are different from those in the rest of the country, where his advisers tell him there needs to be more work at level 4 (first-year degree equivalent).
In a compromise deal, Mr Livingstone's board will set the strategy for post-19 skills training - in effect as another layer of decision-making between the LSC and the Department for Education and Skills.
The LSC retains its full responsibility under the DfES for the funding of 16-19 education in the capital.
Mr Livingstone will be consulted personally on his views about the composition of the new body before recruitment takes place.
The relationship between the LSC and the mayor appears to have thawed since February, when Mr Livingstone said: "The LSC, as currently set up, is unaccountable to Londoners and has failed to deliver for either the unskilled or employers, despite spending around pound;1 billion a year."
David Hughes, the LSC's London regional director, said: "(The GLA and LDA) have been through a sharp learning curve in the past six months about what the LSC does.
"Ken Livingstone will get heard because of who he is, and that has got to be a good thing. This will get more people engaged and excited about skills in a way we could only dream of."