A gel polymer electrolyte based on poly(acrylonitrile-co-styrene) as polymer matrix and N-methyl pyridine iodide salt as I − source was prepared. Controlling the concentration of polymer matrix of poly(acrylonitrile-co-styrene) at 17.5wt.%, mixing the binary organic solvents mixture ethylene carbonate and propylene carbonate with 6:4 (w/w), and the concentration of N-methyl pyridine iodide and iodine with 0.5 and 0.05M, respectively, the gel polymer electrolyte attains the maximum ionic conductivity (at 30°C) of 4.63mScm −1 . Based on the gel polymer electrolyte, a quasi-solid state dye-sensitized solar cell was fabricated and its overall energy conversion efficiency of light-to-electricity of 3.10% was achieved under irradiation of 100mWcm −2 .