A composite proton conducting membrane (PCM) was prepared by radiation-induced grafting (RIG) of binary mixtures of 4-vinyl pyridine (4-VP) and 1-vinylimidazole (1-VIm) onto poly(ethylene-co-tetrafluoroethylene) (ETFE) film followed by phosphoric acid (PA) doping. The grafting parameters such as absorbed dose, temperature, monomer concentration, time, and monomer ratio were varied to control the degree of grafting (DG). The effect of the reactivity ratio of 4-VP and 1-VIm on the composition and degree of monomer unit alternation in the formed graft copolymer was investigated. The changes in the chemical and physical properties endowed by grafting and subsequent PA acid doping were monitored using analytical instruments. The mechanical properties and proton conductivity of the obtained membrane were evaluated and its performance was tested in H2/O2 fuel cell at 120 °C under anhydrous and partially wet conditions. The acid doping level was affected by the treatment parameters and enhanced by increasing DG. The proton conductivity was boosted by incorporating the combination of pyridine and imidazole rings originating from the formed basic graft copolymer of 4-VP/1-VIm dominated by 4-VP units in the structure. The proton conductivity showed a strong dependence on the temperature. The membrane demonstrated superior properties compared to its counterpart obtained by grafting 4-VP alone. The membrane also showed a strong potential for application in proton exchange membrane fuel cells (PEMFC) operating at 120 °C. © 2023 by the authors.