A novel surface modification method was carried out by reactive dc magnetron sputtering to fabricate TiO2 electrodes coated with Al2O3 for improving the performance of dye-sensitized solar cells (DSSCs). The Al2O3-coated TiO2 electrodes had been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-vis spectrophotometer, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The study results revealed that the modification to TiO2 increases dye absorption amount, reduces trap sites on TiO2, and suppresses interfacial recombination. The impact of sputtering time on photoelectric performance of DSSCs was investigated. Sputtering Al2O3 for 4 min on 5-mu m thick TiO2 greatly improves all cell parameters, resulting in enhancing the conversion efficiency from 3.93% to 5.91%. Further increasing sputtering time decreases conversion efficiency. Crown Copyright (c) 2008 Published by Elsevier B.V. All rights reserved.