Cadmium (Cd) is associated with barite; however, its biogeochemical characteristics in environments impacted by barium (Ba) mining are not known. Here, we first revealed the characteristics of Cd concentrations, distributions, and chemical forms in the soil-rice system in Ba mining areas. The associated exposure and risk assessments of Cd via rice consumption were also conducted. Elevated levels of Cd with a wide range of 0.054–91 mg/kg were found in paddy soils, approximately 63% of which exceeded the national Grade II value for soil Cd levels in China (0.3 mg/kg). A significant positive correlation between the soil Cd and soil Ba demonstrated that large amounts of Cd were released into the environment from Ba mining. Cadmium accumulated remarkably in the rice grains (0.007–3.5 mg/kg). The chemical forms in the rice plants indicated that most of the Cd was in the pectate/protein fraction (F2, 92% in the grains and 61–71% in the other tissues), followed by the residual fraction (F3, 7.1% in the grains, 27–38% in the other tissues). A minor portion of Cd was in the soluble and aminophenol fraction (F1, 0.44% in the grains, 0.26–1.4% in the other tissues). The positive correlations observed between the grain Cd and F2 in the roots, stems and leaves suggested that Cd in the rice grain was mainly from F2. Similarly, the root F2 was also positively correlated with that in the stems/leaves, indicating the critical role of F2 in Cd²⁺ migration in rice tissues. The estimated average hazard quotient (2.5) and annual excess lifetime cancer risk (21 × 10⁻⁵ a⁻¹) were higher than the safety levels of 1 and 5.0 × 10⁻⁵ a⁻¹, respectively, showing that the dietary intake of Cd via rice consumption posed high health risks to residents. Our study demonstrated that more concerns should be paid to Cd contamination in Ba mining areas.