Mercury (Hg) exposure in the population from Wuchuan mercury mining area (WMMA), Guizhou, China, was evaluated by human hair Hg investigation. Total gaseous mercury (TGM) in the ambient air and Hg in rice were measured to assess human risk of Hg exposure. High TGM concentrations in the ambient air were found near smelting workshop. Rice not only contained high total mercury (T-Hg) which ranged from 6.0-113 ng/g, but also contained highly elevated methylmercury (Me-Hg) which ranged from 3.1-13.4 ng/g. The means of hair T-Hg concentrations were 33.9 microg/g and 21.5 microg/g at YQG and JXC sites, respectively. Residents from other sites also reflected a certain level of Hg exposure. Age had no significant effect on hair Hg levels, but male had higher hair T-Hg concentrations due to occupational exposure and also higher Me-Hg levels which might be related to larger amount of rice consumption. Hair may be a useful tool for monitoring human exposure of Hg vapor in Hg-mining areas. By a preliminary estimation, the inhalation of Hg polluted air was the main route of inorganic Hg exposure to the smelting workers and vicinal residents; but the population in the study area was also at a potential risk of Me-Hg exposure via rice intake.