For high performance dye-sensitized solar cells (DSSCs), Nanostructural TiO 2 films with large surface area were prepared by the living radical polymerization and sol-gel process. Titania (TiO 2) nanoparticles were surface-modified via atom transfer radical polymerization (ATRP) with hydrophilic poly(metyl methacrylate) (PMMA), which can photodegradable by UV irradiation. Following application of a photodegradation process, sol-gel process and calcination, TiO 2 photoelectrode with Nanostructural TiO 2 were generated. The nanostructural TiO 2 films were used as a photoelectrode in solid-state DSSCs, the energy conversion efficiency was 5.1% at 100 mW/cm 2, which was higher than the value (3.8%) achieved by the pristine TiO 2 photoelectrode. This result is primarily due to the increase of current density resulting from the increased dye adsorption and large surface area.