Composite membrane comprised of the sulfonated poly (aryl ether ketone sulfion) with amino groups (Am-SPAEKS) and poly (vinylalcohol) (PVA) was successfully prepared by the co-solvent coating method. The composite membranes perform a variety of advantages, such as good thermal stability, outstanding water retention, stable mechanical performance and oxidative stability, and the composite membranes have superior water uptake. The proton conductivity of Am-SPAEKS-PVA50% was 0.041 S cm(-1) at 80 degrees C and 0.038 S cm(-1) at 120 degrees C, and the methanol permeability coefficient of the composite membranes was 2.95 x 10(-7) at 25 degrees C and 8.26 x 10(-7) cm(2) s(-1), far below the methanol permeability coefficient of Nafion (25.1 x 10(-7) cm(2) s(-1) at 25 degrees C), so that it could ensures prevent methanol permeation effectively, improve the utilization of methanol. Moreover, the composite membranes show fairly ideal selectivity. These excellent performances show that the composite membranes could be served as new potential membrane materials for direct methanol fuel cells. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.