Biological monitoring for arsenic(As) is usually based upon a determination of urine, blood, nail and hair arsenic concentration, however, saliva has been suggested as a non-invasive biological matrix for assessing exposure. To further evaluate the potential utility of saliva for arsenic biomonitoring, Atomic Fluorescence Spectrometry(AFS-230) and Inductively Coupled Plasma Mass Spectrometer (ICP-MS) were used to evaluate the concentration of arsenic in drinking water, saliva and urine in endemic arsenicosis area in Shanyin County of Shanxi Province. The results showed that the arsenic concentration in drinking water was 0.55-720.0ug/L, and there were 66.67% samples above the arsenic level (50μg/L) of standards for drinking water quality. The median value of arsenic in drinking water was 127.22 μg/L. The salivary and urinary arsenic both can reflect the exposure of arsenic in drinking water. Additionally, there was a significant positive association of salivary arsenic compared with arsenic in drinking water (r=0.674, P<0.05)and urinary arsenic(r=0.794, P<0.05). These results demonstrated that, similar to urinary arsenic, salivary arsenic also can be used as a biomarker for assessing human exposue to arsenic.