The initiative, announced yesterday by Clare Short, Secretary of State for International Development, will allow British teachers to spend a "sabbatical" in classrooms from Bangladesh to Mozambique.
British teachers will be taught how to integrate overseas themes - from poverty to wildlife conservation and Third World music and art - into the national curriculum, said Ms Short, speaking at the annual conference of the Secondary Headteachers Association in Brighton.
Ministers have spent the past year consulting with experts, including Jon Snow, the broadcaster, into how to improve British perception of the Third World.
The department is to give pounds 1,000 grants to UK teachers to cover airfares as part of an pounds 8m budget earmarked for development education. Ministers hope children will learn from the experiences of teachers abroad and integrate the experiences of their partner pupils into school projects.
Research by the Department for International Development has shown that 2,000 schools already want to form partnerships with the Third World.
The "twinning" policy is designed to give British children an insight into other cultures as part of the new curriculum.
The move follows a series of pilot projects run by the British Council which has helped schools set up exchanges, e-mail links and pen pal projects with pupils in the Third World.
One school in Castle Cary, Somerset, has successfully twinned with a school in Zambia. The partnership, sponsored by companies including Adidas, has led to frequent communication between pupils from the schools and visits by teachers.
But a "multicultural" basketball match held in Zambia last year encountered a snag when the British pupils found the basketball court was unfinished. The British school, which had already raised thousands of pounds to fund their students' flights, had to find extra money to buy cement.
"Even though we are in rural Somerset we have a strong commitment to multicultural education," said Laura Tilling of Ansford Community School. "Our students have excellent non-racist attitudes and part of this may be because of our links with Zambia."