Barium (Ba) is a non-essential and toxic element. In China, intensive Ba mining and Ba salt manufacturing have led to sharp increases in Ba in the environment, but little information is available regarding Ba concentrations in paddy soil and rice. The total concentrations and phytoavailability of Ba in paddy soils and paired rice samples collected from the world's largest Ba mine in Dahebian, Tianzhu, Guizhou Province, southwestern China, were investigated. Risk assessments of Ba exposure via rice consumption were also evaluated. The results indicated that extremely high Ba concentrations existed in paddy soils, ranging between 518 mg/kg and 65,760 mg/kg, which demonstrated severe Ba contamination, as expected. The concentrations of rice Ba varied from 0.10 to 3.5 mg/kg, and a significantly positive correlation (r = 0.51, p < 0.05) between rice Ba and water-extractable Ba was observed, suggesting that water, rather than weak acid (0.43 M CH₃COOH), chelating agents (DTPA) or neutral salts (0.1 M NaNO₃, 0.01 M CaCl₂ or 1 M NH₄OAc), is a suitable extractant for predicting the phytoavailable Ba in the studied soils. Risk assessments showed that residents experienced low Ba exposure via rice consumption when considered in isolation of other sources in this study area.