A novel high-performance gel polymer electrolyte (GPE) based on poly(vinylidene fluoride) (PVDF), thermoplastic polyurethane (TPU) and polystyrene (PS) has been prepared. Its characteristics are investigated by scanning electron microscopy (SEM), thermal analysis (DSC), universal testing machines (UTM), galvanostatic charge-discharge and electrochemical impedance spectroscopy. The GPE based on TPU/PVDF/PS (10 wt.%) show a high ionic conductivity of 5.28 x 10(-3) S cm(-1) with the electrochemical stability window of 5.0 V. In addition, its first charge-discharge capacity reached to 169.5 mAh g(-1), high mechanical strength and stability to allow safe operation in rechargeable lithium ion polymer batteries.