The mixed matrix membranes (MMMs) were prepared from crosslinked PDMS incorporated with HF acid etched ZSM-5. ZSM-5 zeolite was etched with a series of HF aqueous-acetone solution and characterized by SEM, BET, XRD and FT-IR. It was found that HF etching process was very effective for removing organic impurities in zeolite and micro-pores were observed out of the surface of zeolite particles, which enhanced the hydrophobicity and surface roughness of ZSM-5 successfully. Both tensile strength and swelling resistance of ZSM-5/PDMS MMMs increased with the rising concentration of HF solution, which can mainly be attributed to the improved zeolite-PDMS interfacial adhesion resulted from the intrusion of PDMS into micro-pores out of the ZSM-5 surface. Subsequently, the sorption experiment was performed with the results suggesting preferential sorption of ethanol by MMMs. Moreover, the sorption selectivity of ZSM-5/PDMS MMMs increased notably as the concentration of HF solution increased. The pervaporation performance of ethanol/water mixtures using MMMs was also investigated in detail. The MMMs filled with etched ZSM-5 showed much better selectivity than that filled with non-etched ones, with a little expense of permeability. It was found that with the same zeolite loading, increasing the HF acid concentration in etching process enhanced the zeolite-PDMS interfacial adhesion which promoted the ethanol selectivity of MMMs, while depressed the total permeation flux a little. In addition, both ethanol permeation and the selectivity increased with an increase of the zeolite loading from 10% to 30%. Nevertheless, excessive zeolite loading or decreasing thickness of selective layer led to the poor selectivity to ethanol. A decline of the ethanol selectivity was also observed as the feed ethanol concentration as well as feed temperature increased. (C) 2012 Elsevier B. V. All rights reserved.