A poly(vinylidene difluoride) (PVDF) membrane was grafted with styrene (St) and maleic anhydride (MAn) using an electron-beam-induced pre-irradiation grafting technique. The grafted membrane (PVDF-g-PS-co-PMAn) was then sulfonated and hydrolyzed to give an ion exchange membrane (denoted as PVDF-g-PSSA-co-PMAc) for vanadium redox flow batteries (VRB) use. Micro-FTIR analysis indicated that PVDF was successfully grafted and sulfonated at the above condition, and the membrane with a high grafting yield (GY) can be easily prepared in a St/MAn binary system at low dose due to a synergistic effect. The water uptake and ion exchange capacity (IEC) of the PVDF-g-PSSA-co-PMAc membrane increased with GY, so too did the conductivity. At a GY of 33.6%, the resulting PVDF-g-PSSA-co-PMAc membrane showed a much higher IEC and conductivity than a conventional Nafion117 membrane, and a much lower permeability of vanadium ions: ca. 1/11 to 1/16 of that through Nafion117. Open circuit voltage measurements showed that the VRB assembled with the PVDF-g-PSSA-co-PMAc membrane maintained values above 1.3V after a period of 33h, which was much longer than that with the Nafion117 membrane. It is expected that this work provides a new approach for the fabrication of ion exchange membranes for VRB.