摘要： As a benchmark photocatalyst, commercial P25-TiO2 has been widely used for various photocatalytic applications. However, the low surface area and poorly porous structure greatly limit its performance. Herein, uniform ordered mesoporous TiO2 microspheres (denoted as Meso-TiO2-X, X represents the rutile percentage in the resulted microspheres) with controllable anatase/rutile phase junctions and radially oriented mesochannels were synthesized by a coordination-mediated self-assembly approach. The anatase/rutile ratio in the resultant microspheres can be facilely adjusted as desired (rutile percentage: 0–100) by changing the concentrations of hydrochloric acid. As a typical one, the yielded Meso-TiO2-25 microspheres have a similar anatase/rutile ratio with commercial P25. But the surface area (78.6 m2 g–1) and pore volume (0.39 cm3 g–1) of the resultant microspheres are larger than that of commercial P25. When used as the photocatalysts for H2 generation, the Meso-TiO2-25 delivers a high solar-driven H2 evolution rate under air mass 1.5 global (AM 1.5G) and visible-light (λ > 400 nm), respectively, which are significantly larger than that of commercial P25. This coordination-mediated self-assembly method paves a new way toward the design and synthesis of high performance mesoporous photocatalysts.