The acquaintance of arsenic concentrations in rice grain is vital in risk assessment. In this study, we determined the concentration of arsenic in 282 brown rice grains sampled from Hainan Island, China, and discussed its possible relationships to the considered soil properties. Arsenic concentrations in the rice grain from Hainan Island varied from 5 to 309 μg/kg, with a mean (92 μg/kg) lower than most published data from other countries/regions and the maximum contaminant level (MCL) for As_i in rice. The result of correlation analysis between grain and soil properties showed that grain As concentrations correlated significantly to soil arsenic speciation, organic matter and soil P contents and could be best predicted by humic acid bound and Fe–Mn oxides bound As fractions. Grain arsenic rises steeply at soil As concentrations lower than 3.6 mg/kg and gently at higher concentrations.