Abstract: Nanoparticles of AgCl were synthesized in W/O reverse microemulsion using ionic liquid 1-dodecyl-3-methyl imidazoium chloride(C₁₂mimCl) as surfactant, methyl methacrylate(MMA)-acrylamide(AM) mixture as oil phase. And then AgCl/poly(MMA-co-AM) hybrid membranes were prepared by microemulsion polymerization for separation of benzene-cyclohexane(mass fraction 50%) mixture by pervaporation at 30℃. The effect of concentration of surfactant (c_C12mimCl) and salt (c_AgNO3) on formation and morphology of AgCl nanoparticles were studied by ultraviolet-visible spectrum and transmission electron microscopy(TEM). The structures of hybrid membranes were characterized by XRD and SEM. The pervaporation performance of the hybrid membranes was studied. The results show that the number and average size of AgCl nanoparticles increase significantly with the increase of c _AgNO3, and the number of AgCl nanoparticles increases but the average sizes decreases with the increase of c_C12mimCl. AgCl nanoparticles maintain well dispersion with small size in AgCl/poly(MMA-co-AM) hybrid membranes. With the increase of c_AgNO3, the flux of the hybrid membranes increases significantly, and the separation factor of hybrid membranes for benzene-cyclohexane mixtures increases first and then decreases. When c_C12mimCl rising, the separation factor increases continuously, and the flux increases first and then decreases. The maximum separation factor of hybrid membrane for benzene-cyclohexane mixtures reaches 5.0 and the flux of the hybrid membrane is 490 g·m^-2·h^-1, which demonstrates good separation property.