Polymer electrolyte membranes (PEMs) are potentially applicable in lithium-ion batteries with high safety, low cost and good performance. Here, to take advantages of ionic conductivity and selectivity of borate ester-functionalized small molecules as well as structural properties of polymer nanocomposite, a strategy of immobilizing as-synthesized polyethylene glycol-borate ester/lithium fluoride (B-PEG/LiF) in graphene oxide/poly(vinyl alcohol) (GO/PVA) to prepare a PEM is put forward. Chemical structure of the PEM is firstly characterized by 1H-, 11B- and 19F-nuclear magnetic resonance spectra, and Fourier transform infrared spectroscopy spectra, respectively, and then is further investigated under consideration of the interactions among PVA, B-PEG and LiF components. The immobilization of B-PEG/LiF in PVA-based structure is confirmed. As the interactions within electrolyte components can be further tuned by GO, ionic conductivity (~10–3 S·cm–1), lithium-ion transfer number (~0.49), and thermal (~273 °C)/electrochemical (>4 V) stabilities of the PEM can be obtained, and the feasibility of PEMs applied in a lithium-ion battery is also confirmed. It is believed that such PEM is a promising candidate as a new battery separator.