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What countries do UN volunteers serve?
Over the years, they have served in about 140 countries. Today 40 per cent are at work in Africa, 26 per cent in Asia and the Pacific, and 15 per cent in Central and Eastern Europe; the remainder are to be found in the Arab States, the Caribbean, and Central and South America. Thirty per cent serve in the world's poorest nations -- the least developed. Half work outside capital cities, frequently in remote towns and villages. This is in response to expressed needs, and it reflects the commitment which volunteers bring. Included here are the field workers serving at the grassroots level in Asia, the Pacific and Africa. These are practitioners with excellent track records in village-level community work; they exchange skills and knowledge among countries of those regions.
The site: http://www.unv.org/
There are Approximately 150 currently. Including, Europe, the middle east, China, Viet Nam, Kyrgyzstan, Lebanon & Guyana. Just to name a few...
If you are interested in doing volunteer work in for the UN. You can always check out the Peace Corps. peacecorps dot gov is a wonderful place to start.
I admire you're wanting to gain further information & dedication to volunteering. Keep up the good work in what ever your endeavors guide you towards.