FeS-coated iron (Fe/FeS) magnetic nanoparticles were easily prepared, characterized, and applied for Cr(VI) removal in simulated groundwater. TEM, XRD, and BET characterization tests showed that FeS coating on the surface of Fe0 inhibited the aggregation of Fe0 and that Fe/FeS at a S/Fe molar ratio of 0.207 possessed a large surface area of 62.1m2/g. Increasing the S/Fe molar ratio from 0 to 0.138 decreased Cr(VI) removal by 42.8%, and a further increase to 0.207 enhanced Cr(VI) removal by 63% within 72h. Moreover, Fe/FeS inhibited the leaching of Fe, reducing the toxicity of the particles. Mechanistic analysis indicated that Fe0, Fe2+, and S2− were synergistically involved in the reduction of Cr(VI) to nontoxic Cr(III), which further precipitated as (CrxFe1-x)(OH)3 and Cr(III)-Fe-S. The process of Cr(VI) sorption by Fe/FeS (S/Fe=0.207) was fitted well with a pseudo-second-order kinetic model, and the isotherm data were simulated by Langmuir isotherm model with a maximum sorption capacity of 69.7mg/g compared to 48.9mg/g for Fe0. Low pH and initial Cr(VI) concentration favored Cr(VI) removal. Continuous fixed bed column studies showed that simulated permeable reactive barriers (PRB) with Fe/FeS was considerably effective for in situ removal of Cr(VI) from groundwater. This study demonstrated the high potential of Fe/FeS for Cr(VI) immobilization in water, groundwater, and soil. Display omitted •FeS coated on Fe0 surface, effectively inhibited Fe0 aggregation, and formed Fe/FeS•Increasing S/Fe molar ratio from 0.138 to 0.207 enhanced Cr(VI) removal by 63%•Fe/FeS inhibited the leaching of Fe, reducing the toxicity of the particles•Fe/FeS removed aqueous Cr(VI) mainly by adsorption, reduction, and precipitation•Fe/FeS effectively removed Cr(VI) through batch and column tests