The total mercury (T-Hg) and methyl mercury (Me-Hg) concentrations in the hair were measured to evaluate mercury (Hg) exposure for the residents in Da-shui-xi Village (DSX) and Xia-chang-xi Village (XCX) in the Wanshan Hg mining area, Guizhou Province, Southwestern China. The mean concentrations in the hair of DSX residents were 5.5 ± 2.7 μg/g and 1.9 ± 0.9 μg/g for T-Hg and Me-Hg, respectively. The concentrations in the hair of XCX residents were 3.3 ± 1.4 μg/g and 1.2 ± 0.5 μg/g for T-Hg and Me-Hg, respectively. Hair Me-Hg concentrations were significantly correlated to T-Hg (r = 0.42, P < 0.01) in the two sites; on average, hair Me-Hg concentration accounted for 40 and 44% of T-Hg for DSX and XCX residents, respectively. Age has no obvious correlation with hair Hg and the hair Hg levels showed a significant gender difference, with higher T-Hg and Me-Hg concentrations in the hair from males than females. The rice collected from the two sites showed high levels of T-Hg and Me-Hg concentration. The results indicated a certain Hg exposure for the residents in DSX and XCX in the Wanshan Hg mining area.