Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride-co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320–490nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10−3 Scm−1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6V with stable interfacial resistance with storage time. The prototype cell shows good charge–discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.