The fabrication of heterojunction between different crystalline phases has been considered to be an effective strategy for promoting charge separation during photocatalytic process. Herein, the mixed-crystalline-phase (MC), spindle-like TiO2 was prepared with a simple hydrothermal method, which was followed by a series of calcination processes. The final products are composed of two crystalline phases including anatase and brookite. The anatase/brookite ratio of the TiO2 is tuned by varying the calcination temperature. The MC TiO2 that consisted of 85.5% anatase and 14.5% brookite has the highest rate of photocatalytic hydrogen evolution (290.2 μmol h −1 ) compared to the purely anatase TiO2. This is attributed to the mixedphase heterojunction structure that improves electron-hole separation, and therefore, enhances the photocatalytic hydrogen production.