By using three configurations of cationic surfactants〔cetyltrimethylammonium bromide(CTAB), Dimethylene-1,2-bis(N-dodecyl-N,N-dimethylammonium bromide)(Gemini 12-2-12) and decamethonium bromide(Bola)〕modified Fe3O4 nanoparticles to produce Fe3O4@CTAB, Fe3O4@Gemini and Fe3O4@Bola (all three are collectively called Fe3O4@surfactants). Respectively, which were used for the treatment of As(Ⅴ) and As(Ⅲ) in water. The morphology was characterized by XRD, TEM, FTIR and magnetic measurement system(VSM), while the adsorption kinetics, adsorption isotherm model fitting and adsorption behavior of As(Ⅴ) and As(Ⅲ) were studied, and the adsorption-desorption regeneration cycle performance and structural stability of Fe3O4@surfactants were investigated. The results showed that the adsorption effect of Fe3O4@surfactants on As(Ⅴ) was higher than that of As(Ⅲ), the adsorption was consistent with the quasi-secondary kinetic model and the Langmuir adsorption isotherm model, and the adsorption capacity of Fe3O4 nanoparticles modified by Gemini 12-2-12 surfactant was the largest. The adsorption driving force of this adsorption process mainly comes from the arrangement behavior of cationic surfactant molecules at the solid-liquid interface, the electrostatic interaction between the surfactant head group and the anion, and the coordination between the tail chain and As(Ⅴ) and As(Ⅲ). The cycle experiment was conducted with As(Ⅴ), which has a high removal efficiency. After five adsorption-desorption cycles, the adsorption rate of As(Ⅴ) by Fe3O4@surfactants was still maintained at about 85%, and the recovery of nanoparticles were all above 90%.