Iron minerals are important for arsenic immobilization in paddy fields; however, intensive ferrolysis causes arsenic (As) release. Bismuth-impregnated biochar derived from wheat straw (BiBC) was synthesized to immobilize arsenic by regulating the ferrolysis process in a paddy field. Further X-ray based analysis (XRD and XPS) results demonstrated that crystal particles of bismuth oxide and bismuth oxychloride were loaded on the biochar surface, helped create additional micropores and improved its specific surface area. The bioavailability of As, as determined via (non)specifically adsorbed As, decreased as the amended dosage of BiBC increased, while wheat straw biochar (WBC) resulted in arsenic release. The presence of biochar caused a faster reduction rate of iron oxides; however, BiBC promoted the sequential co-precipitation of iron and arsenic ions. Adsorption kinetic experiments indicated that ferrous ions facilitated precipitation of As on the surface of BiBC. The XRD analysis of soil samples showed BiBC facilitated the formation/stability of FeOOH. Thus, amendment with BiBC regulated ferrolysis to buffer iron leaching, which contributed to arsenic immobilization under flooding conditions. This study demonstrated the feasibility of As immobilization by metal-impregnated biochar in paddy soils. Display omitted •Bismuth-impregnated biochar (BiBC) decreased the bioavailability of arsenic in paddy soils through regulation of ferrolysis.•Addition of BiBC to arsenic-contaminated soil promoted the reduction of iron oxides.•The reduced iron ions facilitated arsenic adsorption onto the BiBC surface.