In this work, a poly(vinylidene fluoride) (PVDF)-based copolymer is synthesized by grafting two kinds of monomer, 2, 2, 3, 4, 4,-hexafluorobutyl methacrylate (HFMA) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), onto the PVDF powder with pre-irradiation grafting copolymerization. Then a new single lithium-ion conducting polymer electrolyte (SIPE) is prepared by solution casting of the radiation grafted PVDF-based copolymer powder with subsequent lithiation process. Its chemical structure, crystal form, and membrane morphology are characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM), etc. The mechanical properties exhibit the elongation at break of 72% and the tensile strength of 28 MPa. Comparatively high values of ionic conductivity, up to 2.08 x 10(-5)S cm(-1) at 30 degrees C, are obtained, combined with lithium-ion transference number of 0.93 and stable electrochemically oxidation voltage as high as 4.4 V vs Li/Li+. Except for these promising features, the SIPE cell with lithium ion conduction network has a stable charge/discharge cycling performance with various C-rates at room temperature. As-prepared SIPE shows a great prospect for the application in lithium-ion batteries.