The electrochemical properties of the polymer electrolytes based on poly(vinyl chloride)/poly(methyl methacrylate) blend with micro-pore structure have been investigated. The introduction of poly(methyl methacrylate) (PMMA) into the poly(vinyl chloride) (PVC) matrix enhanced compatibility between the polymer matrix and the liquid electrolyte (EC/DMC/LiClO4). The addition of silica into the polymer blend generated a micro-pore structure in the polymer matrix and increased the uptake amount of the liquid electrolyte. The ion conductivity of the polymer electrolyte was increased with the increase in the PMMA content in the blend and the room temperature ion conductivity of the polymer electrolyte based on PVC/PMMA (5:5, w/w) blend was 1.1×10−3 S/cm. The charge–discharge behavior of the unit cell was also investigated.