Hierarchical TiO2 superstructures with desired architectures and intriguing physico-chemical properties are considered to be one of the most promising candidates for solving the serious issues related to global energy exhaustion as well as environmental deterioration via the well-known photocatalytic process. In particular, TiO2 mesocrystals, which are built from TiO2 nanocrystal building blocks in the same crystallographical orientation, have attracted intensive research interest in the area of photocatalysis owing to their distinctive structural properties such as high crystallinity, high specific surface area, and single-crystal-like nature. The deeper understanding of TiO2 mesocrystals-based photocatalysis is beneficial for developing new types of photocatalytic materials with multiple functionalities. In this paper, a comprehensive review of the recent advances toward fabricating and modifying TiO2 mesocrystals is provided, with special focus on the underlying mesocrystallization mechanism and controlling rules. The potential applications of as-synthesized TiO2 mesocrystals in photocatalysis are then discussed to shed light on the structure–performance relationships, thus guiding the development of highly efficient TiO2 mesocrystal-based photocatalysts for certain applications. Finally, the prospects of future research on TiO2 mesocrystals in photocatalysis are briefly highlighted.
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