A new type of a cation exchange membrane named ETFE-g-poly(AA-co-SSS) with bifunctional groups was synthesized by a one-step method. Its preparation by an electron beam-induced pre-irradiation grafting method and the effects of reaction temperature, monomer concentration, pH value of the grafting solution, storage time and temperature of the irradiated poly(ethylene-alt-tetrafluoroethylene) (ETFE) films on the grafting yield were studied. A total concentration of 2 mol L À1 of monomers was found to be beneficial for acrylic acid (AA) and sodium styrene sulfonate (SSS) co-grafting onto the ETFE films.Infrared spectroscopic analysis of the grafted membrane confirmed the existence of sulfonate and carboxylic acid groups. The contact angle of the grafted membrane decreased from 94.3 to 46.7 with the increase in grafting yield. The higher the grafting yield, the faster the response and recovery rate with respect to humidity. AFM images showed that the diameter of the grafted chains on the surface of ETFE membranes was about 30 nm. The voltage of the grafted membrane was stable after 100 cycles of charge-discharge; thus, the prepared membranes have great potentials to be used as separators in secondary batteries.