This study was designed to prepare functionalized multiwalled carbon nanotubes (MWNTs-COOH) incorporated chitosan membrane for separation of ethanol/water mixtures by pervaporation. The pristine MWNTs were treated by mixed acid and then functionalized by diisobutyryl peroxide. The structure and property of the functionalized MWNTs were characterized by Fourier transform infrared and Raman spectroscopies and transmission electron microscopy. A series of functionalized MWNTs incorporated chitosan membranes were prepared by solution blending method. The swelling degree of the resulting membranes. in ethanol/water mixtures was 6 times that of the pristine chitosan membrane. The permeation flux of the membranes increased significantly with increasing functionalized MWNTs content in blend membrane matrix in pervaporation. On the basis of the experiments of sorption equilibrium, the solubility and the diffusion coefficient of membranes in water, ethanol, and 90% ethanol/water mixtures were obtained. Compared with the calculated diffusion coefficient (D-90), the measured diffusion coefficient (D-90(T)) in 90% ethanol/water mixtures was higher, taking M(2) for an example, D-90 was 0.193 x 10(-6) m(2)/s, and D-90(T) was 0.41 x 10(-6) m(2)/s, which indicated the functionalized MWNTs were more prone to increased water permeation when ethanol and water penetrated into the membrane simultaneously. In addition, effects of MWNTs content in the membrane matrix and operating temperature on pervaporation performances were investigated. After introducing functionalized MWNTs, the Arrhenius activation parameters for the total permeation decreased from 28.15 to 12.91 kJ/mol, which indicated that the carbon nanotubes filled membranes were easier to penetrate and exhibited higher flux performance than a pristine membrane.