TiO₂ nanomaterials have attracted tremendous interest in photocatalytic hydrogen generation. Herein we report unique colored anatase TiO₂ hollow spheres consisting of crystalline-inner shell/amorphous-outer shell structured nanocrystallites, which exhibit remarkably enhanced photocatalytic performances for water splitting. The optimized TiO₂ spheres delivered a H₂ production rate of 0.182 mmol g⁻¹ h⁻¹, which was 2 times higher than that of pristine TiO₂. The enhanced activity can be ascribed to the generation of oxygen vacancies and Ti³⁺ sites.