Membranes of poly (ethylene-co-vinyl acetate) crosslinked with dicumyl peroxide (DCP) were prepared. The permeation characteristics in the pervaporation process were examined using chloroform-acetone mixtures. The DCP modified membranes exhibited chloroform permselectivity. The sorption characteristics, effects of feed concentration and crosslinking density on pervaporation were also examined. The separation was found to be maximum at high concentrations of chloroform in the feed mixture. The maximum separation and flux were found to be associated with a moderate amount of crosslinking agent in the membrane. As the crosslinking density was increased, flux and, selectivity were found to decrease.