Abstract: In this work, the characteristics and enhancement of pervaporation for the separation of alcohol-water mixtures especially for ethanol-water azeotrope, have been demonstrated with several kinds of membranes such as CTA, PSf, PVAc/PSf, PAA-PAN/CA, etc. along with the investigation of a modified solution-diffusion model. In addition to the determination of separation factor and permeability, the effective direct determination of solubility of solute (or solvent) inside the membrane was carried out by a novel device coupled with GC-103. Meanwhile, the diffusivity was determined by a transient approach and pervaporation separately. A multicoefficient diffusion model was correlated. The results conform with the theoretical prediction and would provide the scientific basis for further industrial application.