The photocatalytic hydrogen evolution of TiO₂ is deemed to be one of the most promising ways of converting solar energy to chemical energy; however, it is a challenge to improve the photo-generated charge separation efficiency and enhance solar utilization. Herein, black mesoporous rutile/anatase TiO₂ microspheres with a homojunction and surface defects have been successfully synthesized by an evaporation-induced self-assembly, solvothermal and high-temperature surface hydrogenation method. The H500-BMR/ATM (HX-BMR/ATM, where X means the different hydrogen calcination temperatures) materials not only possess a mesoporous structure and relatively high specific surface area of 39.2 m² g⁻¹, but also have a narrow bandgap (∼2.87 eV), which could extend the photoresponse to the visible light region. They exhibit high photocatalytic hydrogen production (6.4 mmol h⁻¹ g⁻¹), which is much higher (approximately 1.8 times) than that of pristine mesoporous rutile/anatase TiO₂ microspheres (3.58 mmol h⁻¹ g⁻¹). This enhanced photocatalytic hydrogen production property is attributed to the synergistic effect of the homojunction and surface defects in improving efficient electron–hole separation and high utilization of solar light. This work proposes a new approach to improve the performance of photocatalytic hydrogen production and probably offers a new insight into fabricating other high-performance photocatalysts.