The Council of Representatives is composed of high-level representatives of the Centre's member countries. It meets annually, and inter-sessionally when required, to examine the work of the Centre and to provide policy and operational guidance. All countries signing and ratifying or acceding to the Agreement are required to appoint a high-level person -- known for commitment and contribution to the development of the South and South-South co-operation -- as their representative to the Council of Representatives. The Council appoints the nine member Board and elects the Centre's Chairperson. The Council elects from among its members a Convenor and a Vice-Convenor.

As of September 2011, the following 51 developing countries have signed, ratified, or acceded to the Intergovernmental Agreement: