The National Association of Head Teachers will use its annual conference in May to launch a project with the charity World Vision, to encourage its members to set up international links.
This week, the NAHT started its campaign by asking eight school leaders to step forward to spend 12 weeks working in Rwandan and Namibian schools. The heads, who will be supported by the charity Voluntary Service Overseas, will offer expertise to their African counterparts, while gaining experience to bring back home.
Last week, Alan Johnson, the Education Secretary, accepted Sir Keith Ajegbo's recommendation that schools should be "active in twinning with other schools of different ethnic, cultural, social and religious backgrounds".
Mick Brookes, general secretary of the association, said twinning schemes could play an important part in teaching citizenship.
"People in this country often depersonalise people from the developing world," he said.
The Department for Education and Skills has already included, in its international strategy, the aim that every school in England should be "enabled" to have a partnership with one overseas.
Around 800 UK schools are involved in the Department for International Development's Global School Partnerships programme, which also promotes twinning. Last year, many schools entered The TES's Make a Link competition, which rewarded successful international partnerships between schools.