This study aimed to describe the distribution of water-arsenic (As) valence states and its relationship to areas with endemic arsenism in the Datong basin. Drinking water samples of patients with endemic arsenism and a control group were examined using hydride generation atomic fluorescence spectrometry (HG-AFS). We analyzed the data using SPSS10.0 for Windows. The As(III)/As ratio was 52.1% in the water sample, exceeding the national standard of 0.05 mg/L. The As(III)/As ratio significantly varied among the different stages in the disease-state groups, and with the control group (χ2 = 22.4, P<0.01). The As(III)/As(V) ratio significantly varied in the four groups (χ2 = 26.19, P<0.01), with a tendency to increase along with the seriousness of the disease state. The most common type of drinking water arsenic valence state was As(III) in the endemic disease-areas. Endemic arsenism was positively correlated with As(III). This led us to conclude that the fraction of each water-arsenic valence state should be studied when determining the arsenic content of drinking water.