Various electrospun poly(methyl methacrylate)/polyvinyl chloride (PMMA/PVC) blend nonwoven membranes were prepared by electrospinning of the blend solutions containing PMMA and PVC in N,N-dimethylformamide (DMF). The electrospun PMMA/PVC had fully interconnected pore structure with high porosity and large specific surface area capable of high uptake of organic liquid electrolyte as gel polymer electrolytes (GPEs). The electrospun PMMA/PVC-based GPEs showed superior electro-chemical properties than PVC-based GPE. Among PMMA/PVC-based GPEs, the 10PMMA/PVC-based GPE comprising 10 wt.% PMMA and 90 wt.% PVC represents the highest ionic conductivity as 7.8 X 10(-3) S cm(-1) and the lowest interfacial resistance as 31.49 Omega with sufficient electrochemical stability of up to 4.7 V. The LiCoO(2)/GPE/graphite cell using 10PMMA/PVC-based GPE retained the discharge capacity of 140 mAh g(-1) after 100 cycles at 0.5C without reducing discharge capacity, while PVC-based GPE showed continuous fading by 110 mAh g(-1). Also, the cell using 10PMMA/PVC-based GPE showed the excellent electrochemical performance caused by the formation of interconnected porous structure and gel state in fibers even at high C-rate (1, 2, 5 C). (C) 2011 Published by Elsevier Ltd.