Pollution of Sb(III) in water has caused great concern in recent years. Nanoscale zero-valent iron (nZVI) can detoxify Sb(III) polluted water, but the rapid passivation and low adsorption capacity limit its practical application. Hence, this study provides a new and efficient nanotechnology to remove Sb(III) using the sulfidated nanoscale zero-valent iron (S-nZVI). The S-nZVI exhibits higher Sb(III)-removal efficiency than pristine nZVI under both aerobic and anoxic conditions. The adsorption capacity of Sb(III) by optimized S-nZVI (465.1 mg/g) is 6 times as high as that of the pristine nZVI (83.3 mg/g) under aerobic conditions. The results indicate that Sb(III) and Sb(V) can be immobilized on the surface of S-nZVI by forming Fe-S-Sb precipitates. Moreover, characterization results demonstrate that the existence of S2− can not only activate H2O2 to produce hydroxyl radical, but also accelerate the cycle of Fe3+/Fe2+ to improve the efficiency of Fenton reaction. Therefore, S-nZVI can produce more hydroxyl radicals to oxidize Sb (III) to Sb (V) and results in 2.3-fold higher oxidation rate of Sb(III) compared to pristine nZVI. The formed FeS layer on the S-nZVI surface can also improve the release ability of Fe2+ and accelerate the formation of nZVI corrosion products. S-nZVI thus holds great potential to be applied in antimony removal.