Soil and house dust collected in and around Hg mines and a processing facility in Horlivka, a mid-sized city in the Donets Basin of southeastern Ukraine, have elevated As and Hg levels. Surface soils collected at a former Hg-processing facility had up to 1300 mg kg−1 As and 8800 mg kg−1 Hg; 1M HCl extractions showed 74–93% of the total As, and 1–13% of the total Hg to be solubilized, suggesting differential environmental mobility between these elements. In general, lower extractability of As and Hg was seen in soil samples up to 12 km from the Hg-processing facility, and the extractable (1M HCl, synthetic precipitation, deionized water) fractions of As are greater than those for Hg, indicating that Hg is present in a more resistant form than As. The means (standard deviation) of total As and Hg in grab samples collected from playgrounds and public spaces within 12 km of the industrial facility were 64 (±38) mg kg−1 As and 12 (±9.4) mg kg−1 Hg; all concentrations are elevated compared to regional soils. The mean concentrations of As and Hg in dust from homes in Horlivka were 5–15 times higher than dust from homes in a control city. Estimates of possible exposure to As and Hg through inadvertent soil ingestion are provided.