A novel configuration of a hollow fiber contained liquid membrane (HFCLM) pervaporation system was used to separate organic solutes such as trichloroethylene and toluene from water. In this system the highly selective organic liquid membrane is contained in the shell side between two sets of hollow fibers packed in a shell-and-tube heat exchanger arrangement. Wastewater is fed into one set of hollow fibers and vacuum is applied in the other set of hollow fibers. The separation factors and solute recoveries for the HFCLM system were higher and water fluxes lower than in a conventional pervaporation system based on silicone rubber with vacuum applied outside the silicone rubber hollow fibers. The effluent concentration data for the HFCLM were satisfactorily correlated with a material balance where the mass flux was expressed in terms of an overall mass transfer coefficient based on resistances-in-series model.