The new division was created from the southern Bakhmut Province of Voronezh Governorate and the self-governed frontier region of Slavo-Serbia, but primarily it was based on the recently created and quickly liquidated lands of the Don Host.

Some of the lands of the Azov Governorate had been acquired by Russia from the Ottoman Empire per the terms of the Treaty of Küçük Kaynarca (signed in 1774) that were lost in 1711 due to the Pruth River Campaign in the Romanian region.

The Azov Governorate was also in charge of a number of fortresses around the Crimean peninsula that Russia received from Ottoman Empire and the city of Kerch which controls the Strait of Kerch and access to the Black Sea.

In 1775: 1776: Beginning around the 1780s, the Azov Governorate was divided into counties (uyezd).

In less than ten years the government of Azov once again was liquidated after it was merged along with the Novorossiysk Governorate into the Vice-royalty of Yekaterinoslav in 1783.