In this article, tert-butylcalix [4]arene (CA)filled poly dimethylsiloxane (PDMS) membranes (CA-fPDMS) were prepared for pervaporative removal of benzene from aqueous solution. In comparison with unfilled PDMS, membrane, CA-f-PDMS membranes showed higher permselectivity towards benzene due to the inclusion interaction between benzene and CA. The separation factor increased from 3275 to 5604 when the CA content varies from 0 to 3 wt % in the PDMS membrane. On the other hand, the normalized permeation rate of benzene (NPRb) decreased with the increase of the degree of crystallization of the membranes due to the crystallinity of CA. The membrane with 1 wt % CA content had the highest degree of crystallization and thus the lowest NPRb, whereas the membrane with 3 wt % CA content was the opposite. Furthermore, the addition of CA increased the elastic modulus of membranes slightly. (c) 2006 Wiley Periodicals, Inc.