Arsenic (As) tends to mobilize in flooded paddy soil due to the reductive dissolution of the iron (oxyhydr)oxides to which As sorbs, resulting in elevated As accumulation in rice that poses a potential risk to the food safety and human health. Microbial sulfate reduction is an important biogeochemical process in paddy soils, but its impact on As mobilization remains poorly understood. In this study, we incubated eight As-contaminated paddy soils under flooded conditions to investigate the effect of sulfate addition on As mobility. Porewater Fe and As concentrations and As species were determined. Among the eight soils, an addition of 50 mg S kg−1 as sodium sulfate decreased porewater arsenite only in two soils, which also showed a high mobilization of Fe2+. Further experiments showed that the addition of sulfate to these two soils stimulated microbial sulfate reduction but decreased porewater concentrations of both arsenite and Fe2+. Additionally, the supply of sulfate increased the fractions of As associated with acid volatile sulfides in the solid phase and decreased As uptake by rice in pot experiments under similar conditions. The effect of sulfate addition on porewater As was diminished by the addition of molybdate, an inhibitor of sulfate reducing bacteria. These results suggest the formation of secondary FeS minerals which co-precipitate or sorb arsenite as a likely mechanism of As immobilization, which was also supported by thermodynamic modeling of the pore water. Thus, sulfate additions can immobilize As and reduce its availability to rice plants in paddy soils containing a high potential for microbial Fe reduction, providing an efficient way to mitigate the As transfer to the food chain. Display omitted •Sulfate addition decreased soluble As(III) in paddy soils with high soluble Fe2+.•Inhibition of sulfate reduction diminished the decrease in soluble As(III).•The decrease in soluble As(III) was due to the adsorption to secondary FeS.•Sulfate addition to paddy soils with high reducible Fe reduced rice grain As. Sulfate addition can reduce As mobility in paddy soils containing a high potential of microbial Fe reduction, offering a potential strategy to mitigate grain As accumulation in these soils.