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 9 wt% polymer solution at room temperature. Then the gel polymer electrolytes (GPEs) are prepared by soaking the electrospun TPU-PVdF blending membranes in 1 M LiClO(4)/ethylene carbonate (EC)/propylene carbonate (PC) for 1 h. The gel polymer electrolyte (GPE) shows a maximum ionic conductivity of 3.2 x 10(-3) S cm(-1) at room temperature and electrochemical stability up to 5.0 V 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 168.9 mAh g(-1) when the gel polymer electrolyte (GPE) is evaluated in a Li/PE/lithium iron phosphate (LiFePO(4)) cell at 0.1 C-rate at 25 degrees 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. (C) 2011 Elsevier B.V. All rights reserved.