A novel alcohol dehydration membrane with a three layer structure has been prepared. The top layer is a thin dense film of chitosan (CS), and the support layer is made of microporous polyacrylonitrile (PAN), Between the dense and microporous layer, there is an intermolecular cross-linking layer. This novel composite membrane has a high separation factor of more than 8000 and a good permeation rate of 0.26 kg/m(2) h for the pervaporation of 90 wt% ethanol aqueous solution at 60 degrees C, 0.8 kg/m(2) h flux for a n-PrOH/water system and around 1 kg/m(2) h flux for an i-PrOH/water system using 80 wt% alcohol concentration at 60 degrees C. The separation factor for both cases is more than 10(5). The separation performance varies with feed composition, operating temperature and conditions of membrane preparation. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, the crosslinking layer improves durability of the composite membrane, and the pervaporation performance can be adjusted by changing the structure of the cross-linking layer. The cross section of the composite membrane has been examined by SEM.