A novel composite membrane using supramolecule calix[4]arene filled polydimethylsiloxane (PDMS) as the top active layer and non-woven fabric as the support layer was developed for the pervaporative removal of benzene from water. Compared to unfilled PDMS homogenous membrane, the composite membrane exhibits both higher separation factor and higher benzene flux by 1.8- and 3.2-folds, respectively. Effects of pervaporation operating parameters such as feed Reynolds number, benzene concentration in feed, downstream pressure and operating temperature on the permeation flux and separation factor had been investigated. The benzene permeation flux was proportional to both the benzene concentration in feed and the downstream vacuum. From the temperature dependent permeation flux values, Arrhenius activation energies for permeation of benzene and water were estimated. (c) 2006 Elsevier B.V. All rights reserved.