Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO4 in EC/PC and showed a high ionic conductivity about 1.6 mS cm-1 at room temperature. The electrochemical stability is at 5.0 V versus Li+/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012