This paper describes the removal of benzene from an aqueous solution of dilute benzene using the poly(methyl methacrylate)-graft-poly(dimethylsiloxane) (PMMA-g-PDMS) membranes containing tert-butylcalix[4]arene (CA) (CA/PMMA-g-PDMS) by pervaporation. When an aqueous solution of 0.05 wt % benzene was permeated through the CA/PMMA-g-PDMS membranes, they showed strong benzene permselectivity. Both the permeability and the benzene permselectivity of the CAIPMNM-g-PDMS membranes were enhanced by increasing the CA content because the affinity of the CA/PMMA-g-PDMS membranes for benzene was increased by introducing CA into the membranes. Transmission electron microscope observations revealed that the CA/PMMA-g-PDMS membranes had a microphase-separated structure consisting of a PMMA phase and a PDMS phase containing CA. An examination of the permeation mechanism led us to the conclusion that the CA in the microphase-separated structure plays an important role as a carrier to selectively partition benzene from the aqueous solution.