A series of poly(vinylidene difluoride)-based amphoteric ion exchange membranes (AIEMs) were prepared by preirradiation-induced graft copolymerization of styrene and dimethylaminoethyl methacrylate in an aqueous emulsion media followed by solution casting, sulfonation, and protonation. The effects of absorbed dose and comonomer concentration on grafting yield (GY) were investigated. The highest GY of 44.5% at a low comonomer concentration of 0.9 M could be achieved. FTIR, TGA, and X-ray photoelectron spectroscopy (XPS) confirmed the successful grafting and sulfonation of the as-prepared AIEMs. Properties of the AIEMs such as water uptake, ion exchange capacity (IEC), ionic conductivity, and crossover behavior of VO2+ ions prepared by this novel technique were systematically investigated and compared with those of the commercial Nafion 115 membrane. It was found that at a GY of 28.4%, the AIEMs showed higher IEC and conductivity, lower permeability of VO2+ ions, and a longer time to maintain open circuit voltage than Nafion 115, which was attributed to their high GY and elaborate amphoteric structure. Consequently, this work has paved the way for the development of green and low-cost AIEMs with good performance for vanadium redox flow battery applications.