From 1596 to 1839, it was a suffragan eparchy of the Metropolis of Kiev, Galicia and all Ruthenia.
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.
[1][2] Due to its proximity to Vilnius, the eparchy played a key role in the church life and many of its bishops later became the Metropolitan bishops of Kiev, a hierarch of the Ruthenian Uniate Church.
Those include Havryil Kolenda, Kyprian Zochovskyj, Lev Zalenskyj and many others.
In the 1800s, the archeparchy was classified by the Catholic Church as a Ruthenian jurisdiction.