The Hg concentrations in 108 samples, comprising 81 coal samples, 1 igneous rock, 2 parting rock samples and 24 water samples from the Huaibei Coal Mining District, China, were determined by cold-vapor atomic fluorescence spectrometry. The abundance and distribution of Hg in different coal mines and coal seams were studied. The weighted average Hg concentration for all coal samples in the Huaibei Coalfield is 0.42 mg/kg, which is about twice that of average Chinese coals. From southwestern to northeastern coalfield, Hg concentration shows a decreasing trend, which is presumably related to magmatic activity and fault structures. The relatively high Hg levels are observed in coal seams Nos. 6, 7 and 10 in the southwestern coal mines. Correlation analysis indicates that Hg in the southwestern and southernmost coals with high Hg concentrations is associated with pyrite. The Hg concentrations in surface waters in the Huaibei Coal Mining District range from 10 to 60 ng/L, and display a decreasing trend with distance from a coal waste pile but are lower than the regulated levels for Hg in drinking water.