Direct methanol fuel cell (DMFC) proton exchange membranes were prepared by blending poly (vinylidene fluoride) (PVDF) with sulfonated poly(ether sulfone) (SPES). Using a diffusion cell and gas chromatographic technique, the effects of PVDF content on methanol permeability in the blended membranes were investigated. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique respectively. The presence of sulfonic acid groups in SPES was confirmed by Fourier transform infrared (FTIR). It was found that the methanol permeability in the blended membranes decreased with PVDF content at the expense of proton conductivity. Blended membranes show methanol permeability values much lower than that of Nafion 115, whereas the proton conductivities of the membranes are comparable with that of Nafion. The thermal stability of these blended membranes is above 250 C, which is sufficiently high for use in DMFC. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 801-808, 2010