Electrospun membranes of polyacrylonitrile are prepared, and the electrospinning parameters are optimized to get fibrous membranes with uniform bead-free morphology. The polymer solution of 16wt.% in N,N-dimethylformamide at an applied voltage of 20kV results in the nanofibrous membrane with average fiber diameter of 350nm and narrow fiber diameter distribution. Gel polymer electrolytes are prepared by activating the nonwoven membranes with different liquid electrolytes. The nanometer level fiber diameter and fully interconnected pore structure of the host polymer membranes facilitate easy penetration of the liquid electrolyte. The gel polymer electrolytes show high electrolyte uptake (>390%) and high ionic conductivity (>2×10−3 Scm−1). The cell fabricated with the gel polymer electrolytes shows good interfacial stability and oxidation stability >4.7V. Prototype coin cells with gel polymer electrolytes based on a membrane activated with 1M LiPF6 in ethylene carbonate/dimethyl carbonate or propylene carbonate are evaluated for discharge capacity and cycle property in Li/LiFePO4 cells at room temperature. The cells show remarkably good cycle performance with high initial discharge properties and low capacity fade under continuous cycling.