Water samples from Xikuangshan (China), the world largest antimony (Sb) mine with a Sb mining and smelting history of more than 200 years, were analyzed. These water samples ranged from stream water in the vicinity of the mining and smelting area that received seepage from ore residues to the underground mine-pit drainage. The concentrations of total Sb, Sb (III) and Sb (V) of the samples were determined by HPLC-ICP-MS. In addition, water pH and concentrations of major cations and anions were analyzed. All 18 samples demonstrated total Sb concentrations with ppm levels from 0.33 ppm to 11.4 ppm, which is two to three orders of magnitude higher compared to the typical concentration of dissolved Sb in unpolluted rivers (less than 1 ppb). This is probably the first time that such high Sb contents have been documented with complete environmental information. Distribution of total Sb and Sb species was investigated, taking into account the respective local environment (in the mining area or close to the smelter, etc.). Sb (V) was the predominant valence in all 18 samples. Only trace levels of Sb (III) were detected in 4 of the 18 samples. Geochemical speciation modeling showed the dominant species was Sb(OH)(6)(-). It is also probably the first time that such high Sb contents have been documented in the natural environment with Sb speciation distribution information. Several potential oxidation pathways are also discussed that might have facilitated the oxidation of Sb (III) in the natural environment. Signs of intoxication were observed among local mine workers with extensive exposure to different forms of Sb for a long period of time.