Pervaporation (PV) membranes made of a chitosan (CS) homogeneous membrane, poly (vinyl alcohol)-poly (acrylonitrile) (PVA-PAN) and chitosan-poly (vinyl alcohol)/poly (acrylonitrile) (CS-PVA/PAN) composite membranes for the separation of ethanol-water solutions were manufactured. The swelling behaviors of CS homogeneous membranes and CS-PVA/PAN composite membranes were measured. Effects of membrane thickness, CS-PVA concentrations in the coating solution, PVA concentrations in the CS-PVA blend polymer, ethanol concentrations in the feed solutions and feed solution temperatures on pervaporation performance for the ethanol-water mixtures are discussed. The experimental results showed that the separation factor (alpha) of CS-PVA/PAN composite membranes increased with an increase of PVA concentration in the CS-PVA blend polymer from 0 to 40 wt%. With an increase in the membrane thickness from 12 to 18 mu m, the separation factor (alpha) of the CS-PVA/PAN composite membrane increased while permeation flux (J) decreased. With an increase of ethanol-water solution temperature, the separation factor (alpha) of CS membranes decreased and the permeation flux (J) of CS membrane increased while for the PVA-PAN and CS-PVA/PAN composite membranes they increased. The apparent activation energy (Delta Ea) of water for CS membranes was 34.3-59.5KJ/mol and less than that of ethanol with 39.4-71.4 KJ/mol. The apparent activation energy (Delta Ea) of water for both PVA-PAN and CS-PVA/PAN membranes was twice as high as that of ethanol. The Delta Ea of water and ethanol for PVA/PAN and CS-PVA/PAN membranes was 13.6-61.6 KJ/mol, 3.3-15.1 KJ/mol, 41.0-60.6 KJ/mol, and 20.9-31.3 KJ/mol, respectively.