Fibrous membranes of composites of poly(vinylidene fluoride (PVDF)/thermoplastic polyurethane (TPU)/poly(propylene carbonate) (PPC) are prepared with different concentrations by electrospinning method. The physical properties of the films are characterized, such as morphology, porosity, thermal stability and mechanical properties. After electrospun films with different concentrations are activated to gel polymer electrolyte (GPE), we test their electrochemical properties. The morphology and the thermal stability of thePVDF/TPU/PPC nanofibers (NFs) with a concentration of 12% are the best. It shows the high tensile strength of 9.9MPa and the maximum elongation of 110.8%. The ionic conductivity of its corresponding GPE is as highas 5.32 mS cm⁻¹, and the electrochemical stability window is up to 5.4 V at room temperature. In addition, it shows a high initial charge capacity of 165.8mAh g⁻¹ and a high initial discharge capacity of 165.1 mAh g⁻¹. The excellent properties make the PVDF/TPU/PPC based GPE (12%) more suitable for lithium-ion batteries