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 880-1260 nm. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of 1 M LiPF(6) in a mixture of organic solvents and the gel polymer electrolyte shows ionic conductivity of 1.7 x 10(-5) S cm(-1) at 20 degrees C. Electrochemical performance of the gel polymer electrolyte at 20 degrees 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. (C) 2011 Elsevier B.V. All rights reserved.