In this study, we report the synthesis and the characterization of poly (vinyl alcohol) based proton conducting membranes. In particular, we describe a novel physically and chemically PVA/HFA (poly (vinyl alcohol)/hexafluoroglutaric acid) blending membranes with BASANa (Benzenesulfonic acid sodium salt) and GA (Glutaraldehyde) as binary reaction agents. The key PEM parameters such as ion exchange capacity (IEC), water uptake, proton conductivity, and methanol permeability were controlled by adjusting the chemical composition of the membranes. The IEC value of the membrane is found to be an important parameter in affecting water uptake, conductivity as well as the permeability of the resulting membrane. Plots of the water uptake, conductivity, and methanol permeability vs. IEC of the membranes show a distinct change in the slope of their curves at roughly the same IEC value which suggests a transition of structural changes in the network. The proton conductivities and the methanol permeability of all the membranes are in the range of 10(-3)-10(-2) S cm(-1) and 10(-8)-10(-7) cm(2) s(-1), respectively, depending on its binary crosslinking density, and it shows great selectivity compared with those of Naflon (R)-117. The membranes display good mechanical properties which suggest a good lifetime usage of the membranes applied in DMFCs. (C) 2013 Elsevier B.V. All rights reserved.