Electrospun, non-woven membrane of high molecular weight poly(acrylonitrile) (PAN) is demonstrated as an efficient host matrix for the preparation of gel polymer electrolytes for lithium-ion batteries. Electrospinning process parameters are optimized to get a fibrous membrane of PAN consisting of bead-free, uniformly dispersed thin fibers with diameter in the range 880–1260nm. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of 1M LiPF6 in a mixture of organic solvents and the gel polymer electrolyte shows ionic conductivity of 1.7×10−5 Scm−1 at 20°C. Electrochemical performance of the gel polymer electrolyte at 20°C is evaluated in lithium-ion cell with lithium cobalt oxide cathode and graphite anode. Good performance with a low capacity fading on charge–discharge cycling is demonstrated.