Core–shell TiO2 microspheres were synthesised by a one step solvothermal method in ethanol solvent. The single anatase TiO2 core–shell structure exhibited high reflectance and large surface area due to its special structure. When applied in the dye-sensitized solar cells (DSCs), this micro-spherical core–shell structure effectively enhanced light harvesting and led to the increase of the photocurrent of the DSCs. As a result, 29% improvement in conversion efficiency of DSCs was achieved after introducing the core–shell TiO2 scattering layer. A comparative experiment between the core–shell structure and a solid structure further confirmed that the core–shell structure is more beneficial for light scattering and photovoltaic performance. The excellent properties of the microspherical core–shell TiO2 make it a promising candidate as a scattering material for DSCs.