Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane was prepared and used for the separation of benzene/cyclohexane mixture by pervaporation processes. The coordination of benzene in the feed with cobalt in the membrane plays a major role in the separation of the mixture. Chelate poly(vinyl alcohol)/poly(allyl amine) blend membrane showed a preferential sorption toward benzene and was found to be more effective for permeating benzene in the benzene/cyclohexane mixture than an original Schiff base poly(vinyl alcohol)/poly(allyl amine) membrane.