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 μm. 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 × 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.