During the archaeobotanical investigation of Scythian-Sarmatian period (Early Iron Age), pits with crop processing waste, discovered in the floodplain of Donets River, eastern Ukraine, and charred remains of cereal grains, dominated by broomcorn millet, were recorded. The grains from the pits were radiocarbon dated to the fifth to first century BC. Those pits are distant from any known contemporaneous settlement. The apparent disconnection of these pits from any local settlement suggests that (1) millet was brought from other locations by mobile groups, or (2) millet was cultivated locally by populations whose settlements have left no discernible archaeological trace. The analysis of molecular biomarkers preserved in palaeosols that are stratigraphically connected to the pits revealed high levels of miliacin, a molecule that can be preserved in ancient soils and sediments, and that is consistent with broomcorn millet (Panicum miliaceum). High levels in miliacin in soils stratigraphically connected to the pits are interpreted as the result of a large biomass of P. miliaceum produced at time of soil formation. Our biogeochemical results applied to a palaeosol thus attest to the in situ cultivation of crops dominated by the broomcorn millet during the early Iron Age in the floodplain of Donets River. Biochemical examination of soils and palaeosols can thus provide useful information on past dynamics of land-use by ancient population, especially when settlements or macrobotanical remains are absent.