A novel polyvinylidene fluoride (PVDF) membrane was fabricated through chemical binding SiO2 nanoparticles (NPs) and copper ferrocyanide (CuFC) layers onto a membrane surface simultaneously to improve the removal efficiency of Cs. The results indicated that the SiO2 NPs were strongly deposited onto the membrane surface, and the CuFC layer was firmly attached on the surface of SiO2 NPs and the membrane. CuFC/SiO2/PVDF membrane remained stable after the acidic solution and sonication stress treatments. CuFC/SiO2/PVDF membrane showed good permeate flux and high selectivity on removal of Cs, and adsorbing capacity reached 1440.4 mg m-2 for Cs. The membrane remained high rejections of Cs in a wide pH, and could be regenerated well by H2O2 and bl(2)H(4). Selective adsorption and electrostatic interaction govern the rejection of Cs. The coexisting cations decreased the rejection of Cs mainly in accordance to the order of cations' hydration radii as 11+ > Na > Ca2+ > Mg2+. In addition, the rejection of Cs could still reach 99.4% in 8 h in the filtration of humic acid solution and natural surface water. The membrane could removal of Cs from water effectively by directly rapid filtration, suggesting it can be applied as promising technology for radioactive wastewater treatment.