Maharashtra tapers in the east, where this district forms the south-east corner. The district is bordered by Gondia district to the north, Rajnandgaon, Kanker, Narayanpur and Bijapur districts of Chhattisgarh to the east, Jayashankar Bhupalpally district of Telangana to the south, and Mancherial and Komaram Bheem districts of Telangana and Chandrapur district to the west.
The district is divided into three sub-divisions: Gadchiroli, Aheri and Desaiganj. These are each further divided into four talukas: Gadchiroli sub-division consists of Gadchiroli, Dhanora, Chamorshi and Mulchera talukas; Aheri sub-division consists of Aheri, Sironcha, Etapalli and Bhamragad talukas; and Desaiganj (Wadsa) sub-division consists of Wadsa, Armori, Kurkheda and Korchi talukas. There are 557 gram panchayats (village councils) and 1,688 Revenue Villages. The district has 12 panchayat samitis (local development-block governments). Only three municipalities, Gadchiroli, Wadsa (Desaiganj), and Armori exist in the district.
Following the delimitation of the constituencies in 2008, the district had three Vidhan Sabha (legislative assembly) constituencies: Gadchiroli, Armori and Aheri. All of these are part of the newly carved Gadchiroli-Chimur Lok Sabha constituency.