In preparation of inorganic particles filled polymer membranes, coupling agents can help to improve the compatibility between inorganic filler and polymer matrix. In this paper, surface modification of silicalite-1 was performed by a coupling agent, vinyltrimethoxysilane (VTMS), and hybrid pervaporation membranes were prepared by incorporating the unmodified or VTMS-modified silicalite-1 into polydimethylsiloxane (PDMS). The VTMS-modified silicalite-1 particles and hybrid membranes were characterized by FT-IR, Si-29 CP MAS NMR, DSC, TGA, XRD and SEM. The results showed that the coupling agent VTMS was readily grafted on the surface of silicalite-1 by hydrolysis reaction and condensation reaction, and the chemical linking between the -CH=CH2 group on the surface-modified silicalite-1 and -Si-H on the PDMS substantially eliminated the nonselective voids inside the membrane. When used to separate acetone, butanol, ethanol (ABE) from aqueous solution, a higher selectivity was obtained with the VTMS-modified silicalite-1/PDMS hybrid membrane. Moreover, the surface modification of silicalite-1 improved its dispersion in PDMS and increased the maximal loading of silicalite-1 in membrane preparation, and thus further enhanced the separation factor of the membrane. (C) 2010 Elsevier B.V. All rights reserved.