The Metropolitan of Kiev, Havryil Kolenda, chose him as coadjutor bishop with right of succession and with the titular title of Vitebsk and Mstyslav, and so he was confirmed by the king on 12 November 1670.

Together with the bishop of Chełm, Jacob Souza, he convened in Lublin a synod in 1680 to try to reconcile the Orthodox and the Greek-Catholics, but because of obstruction by the king and by the Nuncio, the debate never took place.

In the early 1690s founded in Supraśl a Printing press and thus he stopped the influx of liturgical books from Moscow and he arrested the process of latinization.

[2] He was concerned about improving the education of the clergy and the development of a network of schools: for this aim he restored the seminary in Minsk founded by Metropolitan Rutsky.

Zochovskyj expanded the veneration of the Josaphat Kuntsevych, a Greek-Catholic bishop martyred in 1623 by the Orthodox, and moved his feast day from November 12 to September 26.