In the present paper, a method for the determination of trace elements such as Hg and As in biological samples by HG-ICP-AES was presented. Under the optimum experimental conditions and instrumental operation parameters, both the RSDs of Hg and As with the method were below 3%, and the detection limits were 0.6 ng Hg x mL(-1) and 0.8 ng As x mL(-1), respectively, satisfying the demand of detecting trace Hg and As concentration in biological samples. Meanwhile, the analytical results of Hg and As in the national standard reference samples such as human hair (GBW 09101), rice (GBW 08503) and tea leaf (GBW 08505) were in good agreement with the certified values, with RSDs around 5%. Using the HG-ICP-AES method, the concentrations of Hg and As in human hair samples of polymetallic mining area in western Hunan province were determined, and the result shows that human in the mining area was exposed to high levels of Hg and As. The concentrations of Hg and As in the mining area were 1.290 and 1.865 microg x g(-1) respectively, 3.59 and 2.44 times higher than those in the control area, respectively.