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 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M 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) S cm(-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. (C) 2009 Elsevier B.V. All rights reserved.