Effect of poly(ethylene oxide) on the electrochemical properties of polymer electrolyte based on electrospun, non-woven membrane of PVdF is demonstrated. Electrospinning process parameters are controlled to get a fibrous membrane consisting of bead-free, uniformly dispersed thin fibers with diameter in the range of 1.5-1.9 mu m. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of lithium salt in a mixture of organic solvents. The polymer gel electrolyte shows ionic conductivity of 4.9 x 10(-3) S cm(-1) at room temperature. Electrochemical performance of the polymer gel electrolyte is evaluated in Li/polymer electrolyte/LiFePO4 coin cell. Good performance with low capacity fading on charge-discharge cycling is demonstrated. (C) 2013 Elsevier B.V. All rights reserved.