The five form part of a new advisory group intended to provide external expert input and "positive challenge" on developing and implementing policies.
But the Government is having to readvertise to find experts in early years and additional learning needs to sit on the panel.
The new group will meet at least three times a year, with appointed members receiving pound;257 per day for up to 12 days work a year (pound;3,084).
As well as giving policy advice, they will chair subject groups on, for example, early years, 7-14 school standards and improvement, skills and lifelong learning, and curriculum and qualifications. Members of these subgroups will be largely nominated or co-opted.
The five advisers named so far - drawn from 140 applications - are heavily weighted towards post-16 education. They include:
* Sheila Drury, former chairman of the now-defunct post-16 education funding agency, ELWa;
* Huw Evans, principal of Coleg Llandrillo, Colwyn Bay;
* Elizabeth Kidd, who headed up post-16 inspections at Estyn;
* Professor Danny Saunders, head of lifelong learning at the University of Glamorgan.
The only representative of the compulsory education sector in Wales is Bethan Guilfoyle, head of Treorchy comprehensive in the Rhondda. Ms Kidd is a member of the school teachers' review body, which advises the Westminster government on teachers' pay and conditions.
The chairs of the Higher Education Funding Council for Wales, the Wales Employment Advisory Panel, and the former chair of ACCAC, the now defunct Welsh qualifications, curriculum and assessment authority, will also sit on the advisory group, along with Susan Lewis, Wales's chief inspector.
Jane Davidson, education, lifelong learning and skills minister, said: "I wanted a group of individuals who would provide high-quality external advice. I believe we have found them."
The advisory group was set up in part to compensate for the loss of external expertise represented on ACCAC's and ELWa's boards. The quangos were absorbed into the Assembly government's new department for education, lifelong learning and skills on April 1.