The enrichment of cadmium (Cd) in black shale-derived soils is of increasing concern due to its wide occurrence, high Cd concentrations, and potential risks. However, characteristics of enrichment and environmental availability of Cd in these soils are not well understood, which has restricted pollution control and land management. In this study, agricultural soils with elevated Cd concentrations resulting from weathering of Cd-bearing black shale in southwestern China were collected and analyzed. The results showed that Cd could be retained in soils through mechanical inheritance and/or associated with secondary minerals and organic materials. Cd concentrations in soils of the study area ranged between 0.83 and 21.6 mg/kg (average of 5.20 mg/kg), exceeding the risk screening value for agricultural land in China. The heterogeneity of Cd in these soils was highly related to geochemical composition of parent rock and other natural factors. The 0.01 M CaCl2 and 0.05 M EDTA extraction showed that Cd in these soils had high environmental availability and potential risks. Mobile Cd pool (CaCl2 extractable Cd, average: 0.24 mg/kg) accounted for 0.07-38.9% of the total Cd, depending on soil pH. Mobilizable Cd pool (EDTA extractable Cd, average: 2.18 mg/kg) accounted for 22.0-100%. These results showed the significance of geochemical background on enrichment of Cd in soils, documented high environmental availability of Cd in black shale-derived soils, and influence of soil pH.