Antimony (Sb) pollution was an emerging environmental risk in several contaminated waters, whereas its removal still presented as a severe challenge due to the lack of efficient adsorbent and its further removal mechanism. In this study, synthesized absorbents, Fe3O4 magnetic nanoparticles (Fe-MNPs) modified and dispersed with commonly used cationic surfactants, were applied to remove Sb contamination in real surface waters, its synthesized conditions, removal performance and mechanism were investigated by using batch experiments and characterization analyses. Optimum conditions on Sb(V) (the dominant form is Sb(OH)6-) removal by modified adsorbents were obtained as: cetylpyridinium chloride (CPC) coated on Fe-MNPs, mass ratio of Fe-MNPs: CPC = 4:1 and pH = 3-5. Magnetic properties of synthesized adsorbent were not affected, dispersibility was enhanced after fabrication of CPC, that indicated the Fe-MNPs@CPC could be separated and reused with external magnetic field. The adsorption efficiency of this low-cost adsorbent coated with CPC was superior than several traditional adsorbents. The practical application of Fe-MNPs@CPC in five types real waters from the Xikuangshan (XKS) Sb mine area and regeneration experiments by 1 M (mol/L) NaOH solution further confirm its practicability and reusability. Removal experiment results, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) spectra suggested that electrostatic attraction and surface bonding might responsible for the Sb(V) removal by Fe-MNPs modified with cationic surfactants.