Ash as an anthropogenic substrate is widely found at archaeological sites in the south of the East European Plain. Investigations of archaeological ashes, the results of which are presented here, have been conducted in three regions that differ in climate and extent of forest cover (from 29 to 1.5%): 1) typical forest–steppe; 2) piedmont forest-steppe with islands of groves; 3) steppe, almost woodless landscapes. Using spectrometry and X-ray analysis, the present study investigates the chemical composition of ancient ash and ash experimentally produced from different sorts of fuel, as well as the geochemistry of soils developed on ash deposit