The international development charity Voluntary Service Overseas is to stop recruiting newly qualified teachers to work in developing countries.
The UN goal aims for universal primary school education by 2015
Instead, it is launching a recruitment campaign for experienced teachers, head teachers and those with education management skills.
VSO aims to concentrate on helping governments and training colleges improve schools.
New teachers had been filling developments posts for nearly 50 years.
'Life or death'
Volunteers will work in education ministries and teacher training colleges to focus on areas such as national quality standards, curriculum development, monitoring and evaluation, teacher training methodology and school management.
Penny Lawrence, international programmes director at VSO, said: "Anyone working in the UK education sector knows that curriculum relevance, the effectiveness of teacher support and training and the provision of resources has a profound impact on the quality of education a child receives.
"In developing countries, where access to education can literally be a matter of life or death, addressing these issues is crucial."
The National Union of Teachers said it was supporting the move.
A spokeswoman said: "It will give the more experienced teacher a fresh outlook and a new perspective and can reinvigorate them when they return to this country."
However, she warned there was still a shortage of teachers in Britain and said it was important to strike a balance so that not too many teachers went to work overseas, leaving schools short staffed.
The VSO drive is in direct response to one of the United Nation's Millennium Development Goals which aims to provide universal primary education by 2015.
The charity says instead of new teachers, it would prefer applications from more those with more experience, including those aged in their 70s.
The UN's goal aims to ensure all primary school age children can access quality education by 2015.
While an increasing number of poor countries have committed to providing free schooling, systems were already suffering from years of under investment and development.
The move for education is one of eight Millennium Development Goals (MDGs) which range from halving extreme poverty to halting the spread of HIV and Aids.
The blueprint for the goals was agreed by countries worldwide as well as leading development organisations.