The characteristics of polymer electrolytes based on a poly(vinyl chloride) (PVC)/poly(ethyl methacrylate) (PEMA) blend are reported. The PVC/PEMA based polymer electrolyte consists of an electrolyte-rich phase that acts as a conducting channel and a polymer-rich phase that provides mechanical strength. The dual phase was simply developed by a single-step coating process. The mechanical strength of the PVC/PEMA based polymer electrolyte was found to be much higher than that of a previously reported PVC/PMMA-based polymer electrolyte (poly(methyl methacrylate), PMMA) at the same PVC content, and even comparable with that of the PVC-based polymer electrolyte. The blended polymer electrolytes showed ionic conductivity of higher than 10−3 Scm−1 and electrochemical stability up to at least 4.3V. A prototype battery, which consists of a LiCoO2 cathode, a MCMB anode, and PVC/PEMA-based polymer electrolyte, gives 92% of the initial capacity at 100cycles upon repeated charge–discharge at the 1C rate.