Mercury-rich coals in the Donets Basin (Donbas region) of Ukraine were sampled in active underground mines to assess the levels of potentially harmful elements and the potential for dispersion of metals through use of this coal. For 29 samples representing c₁₁ to m₃ Carboniferous coals, mercury contents range from 0.02 to 3.5 ppm (whole-coal dry basis). Mercury is well correlated with pyritic sulfur (0.01 to 3.2 wt.%), with an r² of 0.614 (one outlier excluded). Sulfides in these samples show enrichment of minor constituents in late-stage pyrite formed as a result of interaction of coal with hydrothermal fluids. Mine water sampled at depth and at surface collection points does not show enrichment of trace metals at harmful levels, indicating pyrite stability at subsurface conditions. Four samples of coal exposed in the defunct open-cast Nikitovka mercury mines in Gorlovka have extreme mercury contents of 12.8 to 25.5 ppm. This coal was formerly produced as a byproduct of extracting sandstone-hosted cinnabar ore. Access to these workings is unrestricted and small amounts of extreme mercury-rich coal are collected for domestic use, posing a limited human health hazard. More widespread hazards are posed by the abandoned Nikitovka mercury processing plant, the extensive mercury mine tailings, and mercury enrichment of soils extending into residential areas of Gorlovka.