Crosslinked polydimethylsiloxane/polyetherimide (PDMS/PEI) composite membranes were prepared, in which asymmetric microporous PEI membrane prepared with phase inversion method was acted as the microporous Supporting layer in the flat-plate composite membrane. The different function Composition Of the PDMS/PEI composite membranes were;ere characterized by reflection Fourier transform infrared (FTIR) spectroscopy. The surface and section of PDMS/PEI composite membranes were investigated by scanning electron microscope (SEM). The composite membranes prepared in this work were employed in pervaporation separation of benzene/cyclohexane mixtures. Effects of feed temperature, feed composition, concentration of crosslinking agent oil the separation efficiency of benzene/cyclohexane mixtures were investigated experimentally. In addition, the swelling rate and stableness of composite membrane during long time operation were studied, which should be significant for practical application. The results demonstrated that the pervaporation method could be very effective for separation of the benzene/cyclohexane mixtures. (C) 2009 Wiley, Periodicals, Inc. I Appl Polym Sci 112: 2425-2433, 2009