Nanofibrous membranes for gel polymer electrolytes (GPEs) were prepared by electrospinning a mixture of polyacrylonitrile (PAN) and trimethylolpropane triacrylate (TMPTA) at weight ratios of 1/0.5 and 1/1. TMPTA is used to achieve crosslinking of fibers thereby improving mechanical strength. The average fiber diameters increased with increasing TMPTA concentration and the mechanical strength was also improved due to the enhanced crosslinking of fibers. GPEs based on electrospun membranes were prepared by soaking them in a liquid electrolyte of 1 M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1, v/v). The electrolyte uptake and ionic conductivity of GPEs based on PAN and PAN-acrylate (weight ratio; 1/1 and 1/0.5) were investigated. Ionic conductivity of GPEs based on PAN-acrylate was the highest for PAN/acrylate (1/0.5) due to the proper swelling of fibers and good affinity with liquid electrolyte. Both GPEs based on PAN and PAN-acrylate membranes show good oxidation stability, >5.0 V vs. Li/Li+. Cells with GPEs based on PAN-acrylate (1/0.5) showed remarkable cycle performance with high initial discharge capacity and low capacity fading. (C) 2014 Elsevier Ltd. All rights reserved.