It corresponded to most of modern-day Volyn, Rivne and Zhytomyr Oblasts of Ukraine and some parts of Brest and Gomel Regions of Belarus.

It was created at the end of 1796 after the Third Partition of Poland from the territory of the short-lived Volhynian Vice-royalty and Wołyń Voivodeship.

However, due to the lack of suitable buildings for administrative purposes, the capital was moved once again to Zhitomir (Zhytomyr).

After the Polish-Soviet war in 1920, and according to the Peace of Riga (1921) most of the territory became part of the Second Polish Republic and transformed into the Wołyń Voivodeship, with the capital in Łuck (Lutsk).

The majority of the population indicated Ukrainian[b] to be their mother tongue, with significant Jewish, Polish, German, and Russian speaking minorities.