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 electrochemical properties than PVC-based GPE. Among PMMA/PVC-based GPEs, the 10PMMA/PVC-based GPE comprising 10wt.% PMMA and 90wt.% PVC represents the highest ionic conductivity as 7.8×10−3 Scm−1 and the lowest interfacial resistance as 31.49Ω with sufficient electrochemical stability of up to 4.7V. The LiCoO2/GPE/graphite cell using 10PMMA/PVC-based GPE retained the discharge capacity of 140mAhg−1 after 100 cycles at 0.5C without reducing discharge capacity, while PVC-based GPE showed continuous fading by 110mAhg−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, 5C).