The chitosan doped polyvinyl alcohol film are prepared by blending heating method. The prepared membrane is characterized by Fourier Transform Infrared Spectrometer (FTIR), scanning electron microscope (SEM), atomic force microscope (AFM) and universal testing machine. The surface of the cast membranes is generally flat, and the pervaporation process would cause the membrane to have a wrinkled shape. These membranes can be used for pervaporation to separate methanol/biodiesel mixtures. This paper studies the effects of different chitosan additions, feed temperature and feed concentration on membrane performance. When the chitosan doping amount is 30 % by mass of polyvinyl alcohol at 40°C, the maximum flux reaches 569.212 g m À 2 h À 1 . At the same time, the separation factor increases as the methanol concentration in the liquid decreases. When the methanol mass fraction is 10 %, the separation factor can reach 116.717.