The application of pervaporation (PV) to the removal of volatile organic from aqueous solutions has become very interesting in the last few years. It is caused by the increasing level of compounds, such as petrochemical solvents (benzene, toluene, and xylenes) or chlorinated solvents (trichloroethylene or tetrachloroethylene), which are polluting the natural environment. In this work, effects of polyimide (PI) (prepared by direct polycondensation of dianhydride and diamine followed by thermal cyclization of polyamic acid) filler on PV properties of poly(dimethyl siloxane) (PDMS) have been studied. PDMS membrane filled with PI was used for the separation of benzene (Bz) and toluene (Tol) from the diluted aqueous solution and the results were compared with the neat PDMS membrane of similar thickness. The PDMS-PI membrane showed normalized flux (J') upto 1.2 kg mu m/m(2)h for Bz and 1.48 kg mu m/m(2)h for Tol and selectivity of organics varies from 7.3 to 3.2 for Bz and 8.9 to 2.8 for Tol with increasing concentration of organics. Concentration of PI filler in PDMS varied 5-25% w/w. PI filler increases thermal as well as mechanical stability of filled PDMS membranes. PDMS membrane filled with 25%, PI was chosen for the pervaporation studies. The membranes were characterized by FTIR, thermogravimetric analyser and scanning electron microscopy. The mechanical strength of PDMS filled with 25% w/w PI (SPI-25) membrane was found to be 2.7 MPa. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1967-1974, 2010