Using poly(N-methyl-4-vinyl-pyridine iodide), N-methyl-pyridine iodide and iodine, a solid polymer electrolyte with conductivity of 6.41 mS/cm is prepared. On the basis of a solid polymer electrolyte, a conducting graphite layer, a KI block layer, and a vacuum assembling technique, we achieve an all-solid-state dye-sensitized solar cell with total photoelectric conversion efficiency of 5.64% under AM 1.5 simulated solar light (100 mW/cm(2)) illumination.