Poly(acrylonitrile-co-butyl acrylate) (P(AN-co-BuA))/poly(vinyl chloride) (PVC) blend-based gel polymer electrolyte (BGPE) was prepared for lithium-ion batteries. The P(AN-co-BuA)/PVC BGPE consists of an electrolyte-rich phase, which is mainly composed of P(AN-co-BuA) and liquid electrolyte, acting as a conducting channel and a PVC-rich phase that provides mechanical strength. The dual phase was just simply developed by the difference of miscibility properties in solvent, PC, between P(AN-co-BuA) and PVC. The mechanical strength of this new blend electrolyte was found to be much higher, with a fracture stress as high as 29MPa in dry membrane and 21MPa in gel state, than that of a previously reported P(AN-co-BuA)-based gel polymer electrolyte. The blended gel polymer electrolyte showed ionic conductivity of higher than 1.5×10−3 Scm−1 and electrochemical stability up to at least 4.8V. The results showed that the as-prepared gel polymer electrolytes were promising materials for lithium-ion batteries.