Lithium poly(pyromellitic acid borate) (PPAB) was synthesized via polymerization of lithium tetramethanolatoborate and silylated pyromellitic acid. The synthesized material was characterized by Fourier transformation infrared spectroscopy, B-11 nuclear magnetic resonance, scanning electron microscopy, and thermogravimetric analysis. And electrochemical characterizations were carried out on the blended PPAB/PVDF-HFP membrane. The PPAB-based composite membrane exhibits high lithium ionic conductivity, a broad electrochemical window and a high lithium-ion transference number. The battery cells assembled with the PPAB/PVDF-HFP/EC:PC composite membrane as the electrolyte perform reasonably well not only at elevated temperature but also at room temperature with good cyclability and discharge capacity, making the material suitable for applications in lithium-ion batteries.