Polydimethylsiloxane-ladder like phenylsilsesquioxane copolymer as a novel membrane material has good film-forming ability, high mechanical properties and low swelling capacity. The copolymer membrane displays the permselectivity of organic liquid for the pervaporation of organic liquid/water mixtures. The pervaporation of aqueous solution of ethanol through the membrane has been investigated. High separation factor can be obtained in the range of low ethanol concentration. The flux of ethanol increases and the flux of water keeps constant as the concentration of ethanol in feed increases. The membrane shows good stability of separation at room temperature to 70℃. The comparison of the pervaporation behavior of the aqueous solutions of methanol, ethanol, 2-propanol, acetone, THF reveals that the magnitude of the separation factors and the fluxes increases in the following order: methanol