Two latent chemical cross-linked precursors: (1) oligo-organophosphazene with propionitrile and iodo-(ethylene oxide-co-propylene oxide) and (2) oligo-organosiloxane grafting oligo-ethylene oxide and propylene oxide dimethylamine are synthesized to form all-solid-state polymer electrolyte for dye-sensitized solar cells employing in situ quaterization reaction. This novel electrolyte shows about 6.79×10−7 cm2 s−1 of the apparent diffusion coefficient of triiodide. The disintegrating temperature of 181°C demonstrates good thermal stability of the solid-state electrolyte. Proper amount of 7nm SiO2 modified with 3-triethoxysilylpropyl oligo(oxyethylene-co-oxypropylene) monomethyl urethane is added to the electrolyte and the photocurrent conversion efficiency reaches 2.66% compared with that of 1.81% with no additive.