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.