Characteristics and concentrations of As in Chinese Herbal Medicines (CHMs) from Hebei province (including samples collected from fields and from medicine markets) were investigated, and the ADI (allowable daily intake) standard value from FAO/WHO was used for preliminary assessment of As risk on human health. The results showed that the average of As concentrations in different roots which were used as medicines, ranged from 0.14 mg/kg to 0.54 mg/kg,while for shoots which were used as medicines, average value of As concentrations in Dendranthema morifolium was 1.42 mg/kg, and the range in other species was from 0.09 mg/kg to 0.27 mg/kg. Based on Green Standards of Medicinal Plants and Preparations for Foreign Trade and Economy (2.0 mg/kg), the percentage of samples with As concentrations exceeding standard was 3.27% (n = 153) in roots and 9.09% (n = 44) in shoots,and 4.57% (n = 197) in total CHMs samples. As concentrations in CHMs from fields ranged from 0.03 mg/kg to 0.73 mg/kg,which were all lower than 2.0 mg/kg. However, As concentrations in CHMs from markets ranged from 0.05 mg/kg to 7.05 mg/kg, and the concentrations of As in 6.36% of samples exceeded the limited standard. Arsenic concentrations in samples from markets were significantly higher than those from fields (p < 0.05). As concentrations in Compositae were distributed widely from 0.08 mg/kg to 7.05 mg/kg,and the average at 0.87 mg/kg,while the average of As concentrations in other six families were between 0.21 mg/kg and 0.41 mg/kg, and As levels in 75% of samples for each family were below 0.5 mg/kg. Compared to Compositae samples, the CHMs from other families have higher security. ADI regulated by FAO/WHO was used to assess As risk in CHMs on human health in this study as well. As daily intake through CHMs from markets varied from 0.90 microg/d to 19.7 microg/d, and percentages of the daily intake of As in CHMs to ADI were in the range of 0.70% to 15.4%, which indicated that As in CHMs from markets had a potential risk on human health after intake.