New polymer electrolyte membranes having sulfonic acid groups for polymer electrolyte membrane fuel cell applications were prepared by simultaneous radiation-induced grafting method. The poly(tetrafluoroethylene) (PTFE) films, crosslinked by electron-beam radiation at molten temperature, were used as substrates for grafting of two alkyl vinyl ether monomers, propyl vinyl ether (nPVE) and isopropyl vinyl ether (iPVE), under controlled grafting conditions followed by sulfonation reactions. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), water contact angle and Fourier transform infrared (FT-IR) were used to characterize the crosslinked PTFE (cPTFE) and grafted cPTFE films. The degree of grafting was found to be dependent on the grafting parameters such as irradiation temperature and Lewis acid catalyst, in which in the presence of Lewis acid catalyst or at a temperature close to the boiling point of each monomer, the grafting reaction significantly accelerated even when the relatively low dose was irradiated. Finally, the grafted cPTFE films were sulfonated in a chlorosulfonic acid solution. In spite of the lower ion-exchange capacity (0.75 mmol/g), the membrane synthesized in this study showed a proton conductivity as high as the Nafion 112. (c) 2005 Elsevier B.V. All rights reserved.