Novel pervaporation (PV) membranes for ethanol dehydration were prepared by blend poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCS), followed by the crosslinking reaction with glutaraldehyde; the structure and miscibility of the blend membranes were characterized by Fourier transform infrared, X-ray diffraction, and differential scanning calorimetry; the results indicated that the blends were miscible. The effect of feed concentration, operation temperature, crosslinking agent content, etc. on sorption performance and PV performance of the blend membrane is investigated. The membrane of CMCS/PVA blend ratio of 8 : 2 exhibited a high separation factor of 2959 with a reasonably high water flux value of 0.14 kg m(-2) h(-1) at the azeotropic feed composition (95 wt % of ethanol) at a temperature of 45 degrees C. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 114: 3369-3378, 2009