Nonwoven films of composites of thermoplastic polyurethane (TPU) with different proportion of poly(vinylidene fluoride) (PVdF) (80, 50 and 20%, w/w) are prepared by electrospinning 9wt% polymer solution at room temperature. Then the gel polymer electrolytes (GPEs) are prepared by soaking the electrospun TPU–PVdF blending membranes in 1M LiClO4/ethylene carbonate (EC)/propylene carbonate (PC) for 1h. The gel polymer electrolyte (GPE) shows a maximum ionic conductivity of 3.2×10−3 Scm−1 at room temperature and electrochemical stability up to 5.0V versus Li+/Li for the 50:50 blend ratio of TPU:PVdF system. At the first cycle, it shows a first charge–discharge capacity of 168.9mAhg−1 when the gel polymer electrolyte (GPE) is evaluated in a Li/PE/lithium iron phosphate (LiFePO4) cell at 0.1C-rate at 25°C. TPU–PVdF (50:50, w/w) based gel polymer electrolyte is observed much more suitable than the composite films with other ratios for high-performance lithium rechargeable batteries.