Three-dimensional (3D) crystalline anatase TiO2 hierarchical spheres were successfully derived from Ti foils via a fast, template-free, low-temperature hydrothermal route followed by a calcination post-treatment. These dandelion-like TiO2 spheres are composed of numerous ultrathin nanoribbons, which were subsequently split into fragile nanoflakes as a result of the decomposition of Ti-complex intermediates to TiO2 and H2O at high temperature. The dye-sensitized solar cells (DSSCs) employing such hierarchically structured TiO2 spheres as the photoanodes exhibited a light-to-electricity conversion efficiency of 8.50%, yielding a 28% enhancement in comparison with that (6.64%) of P25-based DSSCs, which mainly benefited from the enhanced capacity of dye loading in combination with effective light scattering and trapping from hierarchical architecture.