A photorelectrode consisting of titania hollow spheres for dye-sensitized solar cells (DSSCs) is prepared by a paste method and the effect of the nanostructure on the performance of DSSCs with non-volatile electrolytes is investigated. The structure of the hollow sphere (HS) electrode with a large pore size and a high porosity allows highly viscous non-volatile electrolytes to penetrate the electrode thoroughly. Furthermore, its outstanding light-harvesting efficiency and long electron diffusion length make the efficiency of the DSSCs with the HS electrode comparable with those of a conventional nanocrystalline electrode, in spite of the smaller amount of the adsorbed dye, when oligomer electrolytes are used. The results show that the structure of a photoelectrode highly improves the performance of the device and the HS electrode is an effective structure for the use of non-volatile electrolytes in DSSCs. (C) 2009 Elsevier B.V. All rights reserved.