In order to develop a novel proton conductive membrane for proton exchange membrane fuel cell (PEMFC), a poly(vinyl di-fluoride) (PVDF) matrix was irradiated with swift heavy ions (SHI) to obtain radically active cylindrical latent tracks in the polymer film. Styrene was then radiografted and further sulfonated into these irradiated cylindrical regions, leading to sulfonated polystyrene (PVDF-g-PSSA) domains within PVDF. The role of the grafting degree and fluence of irradiation of the PVDF matrix on PVDF-g-PSSA membranes properties (chemical composition, ion exchange capacity) was investigated. Then, a membrane-electrode assembly (MEA) was prepared and fuel cell tests have been performed. Our results clearly show that PVDF-g-PSSA membranes with a grafting degree of about 140%, obtained after irradiation at a fluence of 1010 ions/cm2, exhibit good conductivity values but their durability is limited to about 70 h. Decreasing the fluence leads to membranes with lower grafting yield but with fuel cell performances closer to those of 140% grafted PVDF-g-PSSA membrane and improved mechanical properties. Then, ion track grafting technique is a promising technique to obtain PEM with a good trade-off between proton conductivity and mechanical properties.