Previously an Eastern Orthodox eparchy founded in 992 and headed by a suffragan bishop of the Kiev Metropolitan in Vilnius, in 1596 the eparchy of Polotsk, entered in full communion with the Catholic Church as a Greek Catholic Church through the Union of Brest. The eparchy was among the first that joined the union in 1596 along with eparchies of Kiev, Pinsk, Lutsk, Volodymyr and Kholm. Due to the Union of Brest, Belarus, the former Orthodox Church became known as the Ruthenian Uniate Church.
To the archeparchy of Polotsk were later added the territories of the eparchy of Mstislav (also of 13th-century origin) and the 10th-century eparchies of Orsha and Vitebsk.[1][2]
Markian Bilozor (1697 - death 18 June 1707); previously Coadjutor Bishop of Pinsk–Turaŭ of the Ruthenians (Belarus) (? – 1665), succeeding as Eparch (Bishop) of Pinsk–Turaŭ of the Ruthenians (1665 – 1697)
Sylvester Peshkevych (9 November 1710 - death 8 September 1714)
Florian Hrebnitskyj (1715 - death 18 July 1762)
Jason Smogorevskyj (18 July 1762 - 25 June 1781), succeeding as former Coadjutor Archbishop of Polatsk–Vitebsk of the Ruthenians (? – 1762.07.18); later Metropolitan Archbishop of Kyiv–Halyč of the Ukrainians (Ukraine) (1781.06.25 – death 1788)
^Kazimierz Dola, "Katalog arcybiskupów i biskupów rezydencjalnych eparchii polskich obrządku grecko-unickiego od Unii Brzeskiej (1596) do roku 1945" in Historia Kościoła w Polsce t. II 1764-1945, cz. 2 1918-1945, Poznań-Warszawa 1979, p. 308