Au@TiO₂ hollow submicrospheres with controllable sizes and shell thicknesses are easily synthesized by the hydrothermal method. When Au@TiO₂ hollow submicrospheres are used as the photoanodes of DSSCs, a power conversion efficiency of 8.13% is achieved, which exhibits a 30% increase compared with the conventional DSSCs fabricated with P25 TiO₂ photoanodes.