Transport of liquids by pervaporation takes place by a solution—diffusion mechanism. In order to investigate the “solution part” of this transport model, preferential sorption has been compared with preferential permeability. Sorption equilibria and pervaporation experiments for the systems water—ethanol—cellulose acetate, water—ethanol—polyacrylonitrile and water—ethanol—polysulfone have been investigated. Theoretical values of preferential sorption have been derived from Flory—Huggins thermodynamics, extended with concentration dependent interaction parameters. These calculated sorption values show a reasonable agreement with experimental values. The large difference in molar volumes between water and ethanol determines the preferential sorption of water in these systems to a great extent, and this effect increases with decreasing swelling value. Comparison of preferential sorption experiments with pervaporation experiments indicates that, apart from the effect of differences in diffusivity for the permeating components, preferential sorption contributes to a major extent to selective transport.