AgCl nanoparticles were synthesized in a water-in-oil microemulsion using the ionic liquid 1-dodecyl-3-methyl imidazoium chloride (C(12)mimCl) as the surfactant and methyl methacrylate-acrylamide (MMA-AM) mixture as the oil phase. An aqueous AgNO3 solution was added to the microemulsion as the source of Ag+ ions. Subsequently, AgCl/poly(MMA-co-AM) hybrid membranes were prepared by in situ microemulsion polymerization, and applied for pervaporation of mixtures of benzene and cyclohexane. The effects of C(12)mimCl (C-C12mimCl) and AgNO3 (C-AgNO3) concentrations on the formation and morphology of AgCl nanoparticles were studied. The structure of AgCl/poly(MMA-co-AM) hybrid membranes was examined and analyzed with SEM and XRD. The swelling-sorption behavior of AgCl/poly(MMA-co-AM) hybrid membranes in the benzene and cyclohexane solutions, and their separation ability were measured. The AgCl nanoparticles that were formed in the ionic liquid-based microemulsion were found to be spherical with a mean diameter of 20 nm within a narrow size range. The number of AgCl nanoparticles increased with increasing C-C12mimCl, and the mean diameter of the AgCl nanoparticles increased with increasing C-AgNO3. The AgCl/poly(MMA-co-AM) hybrid membranes were found to have a core-shell structure with AgCl as the core and poly(MMA-co-AM) as the shell. The AgCl nanoparticles were uniformly dispersed in the poly(MMA-co-AM) matrix. The AgCl/poly(MMA-co-AM) hybrid membranes displayed the characteristics of preferentially selective sorption-swelling benzene and demonstrated better pervaporation performance than that of the membrane without nanoparticles in separating the benzene/cyclohexane mixture. (C) 2013 Elsevier B.V. All rights reserved.