Volodymyr Vasylenko graduated from Law Department of Kiev National Taras Shevchenko University in 1959 and completed the postgraduate of the International law in 1964.
1972-1992 – was a scientific consultant of the Ministry of Foreign Affairs of Ukraine for law issues. At the end of the 1989 was taking part in development of legal basis for economic independence of Ukraine. In spring 1990 prepared the first draft of the Declaration of State Sovereignty of Ukraine and therefore as a consultant of the Verkhovna Rada of Ukraine was taking part in elaboration of the final version of the Declaration.
Since 1992 Volodymyr Vasylenko – Ambassador in Benelux countries and also the Representative of Ukraine to the EU and NATO and during 1998-2002 – Ambassador of Ukraine to the Great Britain and Northern Ireland.
1991-2009 – repeatedly took part in the General Assembly of the UN as an expert, advisor, member of the delegation of Ukraine and was representing Ukraine in Third Committee (human rights) and Sixth Committee (legal issues).
In 2001 he was elected by the General Assembly of the UN to the International Criminal Tribunal for the former Yugoslavia where he has been working in a capacity of a judge until 2005.
2006-2010 Mr. Vasylenko was the Representative of Ukraine to the United Nations Human Rights Council.
2008 – Representative of Ukraine to the International Court of Justice of the UN during the session of Rumania-Ukraine issue.
He is also Member of the Peoples Committee for Defense of Ukraine.