Novel upconversion NaYF4:Yb3+,Er3+/TiO2 core-shell nanoparticles (NPs) are synthesized and used to prepare the photoelectrode (PE) of dye-sensitized solar cells (DSSCs). The morphology, structure, photoluminescence characterization of the NaYF4:Yb3+,Er3+/TiO2 core-shell NPs and the photoelectric performance, alternating current impedance spectroscopy of DSSCs are characterized using transmission electron microscopy, X-ray diffraction, upconversion luminescence (UCL) spectrofluorimetry and electrochemistry. Compared with the pure TiO2 PE or the NaYF4:Yb3+,Er3+ upconversion NPs and TiO2 simply mixed prepared PE as the volume ratio of the core-shell structure, the DSSCs with the upconversion core-shell PE show a greater photovoltaic efficiency. The energy conversion efficiency of the DSSCs with a NaYF4:Yb3+,Er3+/TiO2 PE is 23.1% higher than with a pure TiO2 PE and 99.1% higher than with a mixed PE using the same conditions. This enhancement is due to the UCL core extending the spectral response range of DSSCs to the infrared region and their particular shell structure, retaining its semiconductor character. This method represents a novel approach to increase the efficiencies of DSSCs. (C) 2012 Elsevier B.V. All rights reserved.