Diplomatic relations between the EU and Ukraine were established in December 1991. Next year Ukraine designated its first representative to the EU - Ambassador Volodymyr Vasylenko.

The fully-fledged Mission of Ukraine to the European Union was established in Brussels in 1996. Since then, it has been headed by Ukraine's high-rank diplomats and officials: 

Ihor MITYUKOV (1996 - 1998), former Deputy Prime-Minister of Ukraine; 

Boris HUDYMA (1998 - 2000), career diplomat, former Deputy Minister of Foreign Affairs responsible for the relations with the European Union institutions; 

Roman SHPEK (2000 - 2008), former Deputy Prime Minister and Head of the National Agency for Development and European integration; 

Andri VESELOVSKY (2008 - May 2010), career diplomat, former Deputy Minister of Foreign Affairs responsible for the relations with the European Union institutions; 

Kostiantyn YELISIEIEV (July 2010 - July 2015), career diplomat, former Deputy Minister of Foreign Affairs responsible for the relations with the European Union institutions.

Mykola TOCHYTSKYI (4 February 2016 – 6 April 2021) - career diplomat, former Permanent Representative of Ukraine to the Council of Europe, Head of the General Service on International Cooperation, Secretariat of the President of Ukraine. 

Vsevolod Chentsov (appointed on August 25, 2021) - career diplomat, Ambassador Extraordinary and Plenipotentiary of Ukraine to the Kingdom of the Netherlands, Permanent Representative of Ukraine to the Organization for the Prohibition of Chemical Weapons (2017 - 2021).