To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), four styrene derivative monomers, m,p-methylstyrene (MeSt), p-tert-butylstyrene (tBuSt), divinylbenzene (DVB) and bis(p,p-vinyl phenyl) ethane (BVPE) were graft copolymerized into poly (ethylene-co-tetrafluoroethylene) (ETFE) films followed by sulfortation and hydrolysis. The latter two monomers were used as crosslinkers. The graft copolymerization was carried out by the gamma-ray preirradiation method. The influence of the preirradiation dose and the grafting kinetics were investigated in detail. Sulfonation of the grafted ETFE films was performed in a chlorosulfonic acid solution, by which the sulfonation ratio reached about 90%. By means of the FT-IR and TG-DTA measurements, it was evident that the monomers were grafted into the ETFE films and that the sulfonic acid groups were attached to the aromatic rings of the graft chain. Assessing their potential to serve as polymer electrolyte membrane in a DMFC was performed by measurement of the ion exchange capacity, proton conductivity, water uptake, chemical stability and the methanol permeability. The newly obtained membrane possesses significantly higher chemical stability than the traditional styrene/DVB-grafted membrane and six times lower methanol permeability compared to the Nafion((R)) 112 membrane. Therefore, this study reveals the possibility of the developed inexpensive four monomers-grafted membranes, which could provide an attractive alternative as a substitute for the expensive Nafion((R)) membranes for DMFC applications. (c) 2005 Elsevier B.V. All rights reserved.