In order to assess soil As contamination and potential risk for human, soil, paddy rice, vegetable and human hair samples from the areas near the industrial districts in Chenzhou, southern China were sampled and analyzed. The results showed that the anthropogenic industrial activities have caused in local agricultural soils to be contaminated with As in a range of 11.0-1217 mg/kg. The GIS-based map shows that soil contamination with As occurred on a large scale, which probably accounted for up to 30% of the total area investigated. Soil As concentration abruptly decreased with an increase in the distance from the polluting source. High As concentrations were found in the rice grain that ranged from 0.5 to 7.5 mg/kg, most of which exceed the maximal permissible limit of 1.0 mg/kg dry matter. Arsenic accumulated in significantly different levels between leafy vegetables and non-leafy vegetables. Non-leafy vegetables should be recommended in As-contaminated soils, as their edible parts were found in relatively low As level. Arsenic concentrations in 95% of the total human hair samples in the contaminated districts were above the critical value, 1.0 mg/kg, set by the World Health Organization. Arsenic could be enriched in human hair to very high levels without being affected by As containing water. The results revealed that the soils and plants grown on them are major contributors to elevate hair As in the industrial population. Therefore, the potential impact on human health of ingestion/inhalation of soil As around the industrial districts seems to be rather serious. Hence proper treatments for As contaminated soils are urgently needed to reduce the contamination.