To overcome the strong dependence of the conductivity on the relative humidity and the lower thermal stability at high temperature of perfluorosulfonate polymers and the leaching-out problem of phosphoric acid doped membranes, a series of phosphorylated and crosslinked poly(vinyl alcohol) (PVA)/bisphenol A-epoxy resin [diglycidyl ether of bisphenol A (DGEBA)] membranes were prepared. The membrane properties were characterized by Fourier transform infrared spectra, solubility, thermogravimetric analysis, water uptake, swelling ratio, ion-exchange capacity (IEC), small-angle X-ray scattering, and proton conductivity measurements. The results show that the crosslinked PVA/DGEBA membrane had a higher thermal stability (T d ! 250 C) than the pure PVA membrane (T d ! 220 C) and that the phosphorylated and crosslinked PVA/DGEBA membranes (IEC ¼ 5.54 mmol/g) with a low volume swelling ratio (7.21%) could achieve a maximum proton conductivity of 2.51 Â 10 À3 S/cm at a temperature as high as 150 C in anhydrous conditions V C 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122: [3071][3072][3073][3074][3075][3076][3077][3078][3079] 2011