The pervaporation behaviors of aqueous ethanol mixtures through the poly(ethylene oxide) (PEO)/chitosan (CS) blend membrane were investigated. The results show that both CS and PEO/CS membrane preferentially permeate ethanol at a lower alcohol concentration in feed, and the selectivity of CS membrane toward alcohol can be greatly improved by introducing hydrophilic polymer PEO into CS. The PEO/CS blend membrane gave a separation factor of 4.4 and a flux of 0.9 kg m(-2) h for 8 wt % of ethanol in the feed at 20 degrees C. At the same time, the reason introducing PEO can improve alcohol-permselectivity of CS membrane is explained on the basis of experimental data. Blending with PEO made the structure of CS chain looser, which resulted in ethanol molecules passing through easily, on the other hand, strengthened the ability of forming water clusters that inhibit the permeation of water molecules. From the experimental results, although the PEO/CS blend membrane was not a usable membrane with high selectivity to alcohol, a new method to prepare alcohol-permselective membranes appears to be developed by modifying hydrophilic polymers.