A series of sulfonated poly(aryl ether ketone sulfone)/poly(vinylidene fluoride) phosphotungstic acid (SPAEKS/PVDF-HPW) composite membranes were prepared and characterized by Fourier transform infrared spectroscopy. No phase separation was observed by scanning electron microscopy. The HPW particles are evenly dispersed in the membranes, probably because the microporous structure of PVDF stabilized the dispersion of HPW particles in the membranes. Thermogravimetric analysis showed that the thermal stability of the membranes increased with increase in HPW content. Moreover, the composite membranes exhibited outstanding oxidative stability. The methanol permeability coefficient of the SPAEKS/PVDF-HPW10% membrane at 20 degrees C was 1.68 x 10(-7) cm(2) s(-1), and the highest proton conductivity of the membrane at 80 degrees C was 0.098 S cm(-1), slightly lower than that of Nafion (R) 117. However, the relative selectivity of the membrane was higher than that of Nafion (R) 117. The swelling ratio of the membrane at 80 degrees C was 16%, and the methanol uptake of the membrane at room temperature was only 10.2%, much lower than those of Nafion (R) 117. The results indicate that the SPAEKS/PVDF-HPW membranes can be used as an alternative proton exchange membrane for direct-methanol fuel cells. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.