Although thallium (Tl) is a high toxic element, little information is available on the environmental risks of Tl in agricultural soils with intensive practices, particularly nearby mining sites. Therefore, we investigated the potential release of Tl in acidic soils with intensive cultivation nearby a waste copper mining site from southern China based on its level and chemical fractions as well as simulated release under artificial acid rain. Results showed that the average Tl content was 1.31 mg/kg in the studied area, which significantly exceeds permissible thallium value of 1 mg/kg for agricultural soil in China. Some vertical increases of soil Tl from different land uses indicate the potential transport of Tl downward to groundwater. High positive correlations between surficial soil Tl and rubidium (Rb) and copper (Cu) indicated that Tl has the lithophile and chalcophile behavior. Tl in soils mainly entrapped in residual fraction. The exchangeable fraction of Tl in agricultural soils was less than undisturbed natural soils and copper mined soils. Additionally, the percentage of Tl release from undisturbed natural soils and soils of copper ore area was more than that from agricultural soils in simulated acid rain. Furthermore, the releases of Tl from the soils increased with the acidity of artificial acid rain. Thus, more attentions must be paid to land management of this similar area to avoid the risk of Tl impact on human healthy.