Surface crosslinked chitosan composite membranes were prepared with glutaraldehyde and surfuric acid. Effects of neutralization for complex between chitosan and acetic acid and of water permeability for substrate membranes on pervaporation performance were investigated. For ionically crosskinked membranes, effect of active layer thickness on separation factor of water/ethanol mixture was studied. With increasing the water permeability of the substrate, the membrane showed an increased separation factor, while it maintained a constant permeate flux. Neutralized chitosan composite membranes revealed a decreased separation factor and a constant permeate flux. When the thickness of the active layer increased, an optimum crosslinking time to achieve higher separation factor shifted to a prolonged times.