On the first relations of the Holy See to the public entities that existed on the territory of Ukraine, it is known from the end of 10th century. Enhance relations between the See of Rome and Ukraine of the 13th century. Pope Innocent IV in 1253, presented the Prince Daniel of Galicia crown. Diplomatic relations with the Holy See supported the West Ukrainian People's Republic, in May 1919, its ambassador, Count Michael Tyszkiewicz received Pope Benedict XV, February 23, 1920 by Giovanni Genocci was appointed Apostolic visitator in Ukraine. After the onset of the Bolsheviks in 1921, he returned to Rome. Diplomatic relations between the independent Ukraine and the Holy See were established February 8, 1992. On this day, Pope John Paul II issued briefs «Ucrainam Nationem», where he founded the Apostolic Nunciature in Ukraine. On 28 March 1992, John Paul II appointed Archbishop Antonio Franco the first apostolic nuncio in independent Ukraine. Archbishop Nikola Eterovic was appointed the second apostolic nuncio in Ukraine in 1999. On 22 March 2004, Archbishop Eterovic left Ukraine. Archbishop Ivan Jurkovic was the third nuncio in Ukraine appointed in 2004.
In 2011 Pope Benedict XVI has appointed apostolic Archbishop Thomas Gullickson, titular Archbishop of Bomarzo, as nuncio in Ukraine.