Based on the Memorandum of Understanding and Note on Guiding Principles signed in 2003, UNV and the United Nations Department of Peacekeeping Operations (DPKO), together with the newly formed Department of Field Support (DFS), are also working together to ensure volunteerism is recognized as a significant element in the success of UN peacekeeping operations. DFS was established in 2007 to address the UN's growing peacekeeping responsibilities.

In 2007, about 3,000 UN Volunteers – almost half of all UN Volunteers – supported 18 peacekeeping and special political operations in fulfilling their mandates. Their roles vary enormously. Some are in 'substantive functions', areas such as civil affairs, human rights, demobilization and reintegration. They are often community-based and operate in close cooperation with local and national authorities. Others work in technical support for logistics, transport and communications, internal services without which the missions could not function.

Below are some of their stories.