Hydrophobic polymer possesses significant potential for selective separation of volatile organic compounds (VOCs) from their aqueous solutions by pervaporation (PV). In the present study mixed matrix hydrophobic membranes of polydimethylsiloxane (PDMS) supported on polyvinylidenefluoride (PVDF) substrate were synthesized by incorporating hydrophobic inorganic ZSM-5 filler. The indigenous membranes were crosslinked with tetraethylorthosilicate (TEOS) for the extraction of volatile chlorinated hydrocarbons such as dichloromethane (DCM), trichloromethane (TCM), 1,2-dichloroethane (DCE), and 1,1,2,2-tetrachloroethane (TeCE), which pose serious environment threat and health hazard. Thermal stability, crosslinking, crystallinity, surface morphology and swelling characteristics of the indigenously developed membranes were determined by TGA, FTIR, XRD, SEM and sorption studies, respectively. Effect of operating parameters such as feed composition and filler concentration on separation performance in terms of flux and selectivity were determined. Flux of DCM, TCM, DCE and TeCE was found to be 0.166, 0.146, 0.141 and 0.06 kg m(-2) h(-1) with selectivity of 541, 1068, 917 and 15,000, respectively, for 20% ZSM-5 filled PDMS membrane for aqueous feeds containing 1.33% (w/v) DCM, 0.8% (w/v) TCM, 0.84% (w/v) DCE and 0.28% (w/v) TeCE in water. The membrane exhibited considerable feasibility for scale-up with significant potential for removal of hazardous chlorinated VOCs from aqueous solutions. (C) 2013 Elsevier B.V. All rights reserved.