The raion has an international border with the Russian Federation (Rostov Oblast) to its east and south (still not established), Starobesheve Raion to its southwest, cities of Donetsk and Makiivka to the west, and Shakhtarsk Raion to its north.
Within the Amvrosiivka Raion there is: one city (Amvrosiivka), 3 urban-type settlements (Kuteynykove, Novoamvrosiivs'ke, and Voykovskyi), 30 selsovets, and 43 settlements.