Novel single-ion conductor polymer (SCP) membranes based on oxalate-chelated borate structure grafted polyvinyl formal (PVFM) were developed herein. The membranes and their application as polymer electrolytes for lithium-ion batteries were characterized by Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetry (TG), differential scanning calorimetry (DSC), stress–strain test, electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV) and charge/discharge test. Results show that the novel SCP membranes exhibit good thermal stability and excellent mechanical strength of 11–34MPa; the obtained gel polymer electrolytes (GPEs) from propylene carbonate (PC) plasticized SCP membranes show ionic conductivity of 10−6–10−5Scm−1 between 15 and 60°C, wide electrochemical stability window of >5V (vs. Li+/Li) and good matching properties with Li/LiFePO4 cells. The PVFM based SCP membrane shows promising characteristics as polymer electrolytes for lithium-ion batteries.