Traditionally, the pervaporation of water-solvent mixtures where the solvent is the major component is performed using hydrophilic membranes (such as PVA or zeolites). In the present paper a new type of pervaporation membrane (amorphous perfluorinated polymer, hydrophobic) was studied for the separation of water-solvent mixtures. This membrane has high free volume and is inert for all solvents, and has a remarkable mechanical, chemical and thermal stability. The water is transported by solution diffusion model and the separation of solvent is primarily based on molecular sieving (size exclusion) principles. The membrane shows a high stability for operation over a broad range of feed concentrations without swelling: the operating temperature does not have a significant effect on membrane separation performance. Separation factors as high as 349 and 500 for water-ethanol and water-IPA mixtures (2-98 wt.% water-solvent) and fluxes of 0.15 and 0.05 kg/(m(2) h), respectively were obtained at 22 degrees C. The permeance-based selectivities were also calculated, and the selectivity is approximately constant for a wide range of feed concentrations. The pervaporation of more complex (ternary) mixtures of water-ethanol-ethyl acetate showed that this system could be successfully applied for solute separation based on size exclusion. (C) 2010 Elsevier B.V. All rights reserved.