Various polymer materials were chosen as candidate pervaporation membranes for selective removal of ethanol and chloroform from aqueous binary solutions. Flat sheet membranes were cast from polymer solutions and evaluated for their sorption, diffusion and pervaporation of organics from dilute aqueous solutions. Several apolar polymer materials exhibit higher separation coefficients than that expected from vapor-liquid equilibrium for chloroform and ethanol. Selective sorption of organics and water appears to dominate pervaporation selectivity of different polymers. Independent measurements of organic and water sorption and the preferential sorption theory both give good correlations with separation factors. The product of independently measured distribution and diffusion coefficients correlates with the measured permeability coefficients of pervaporation of organics from dilute aqueous solutions. This supports the solution-diffusion mechanism of transport in the membranes tested.