Beyond Static Perspective: Deciphering Light‐Induced Structural Evolution and Its Regulation on Photocatalytic Efficiency and Stability

ABSTRACT Photocatalytic technology stands as a pivotal avenue for addressing global energy and environmental challenges, but its practical use is hindered by insufficient efficiency and unclear mechanisms of reaction active sites. Emerging research has unveiled that upon exposure to light, photocatalysts undergo in situ structural evolutions, including light‐driven structural construction, real‐time reconstruction of structures and active sites during catalysis, and unavoidable photoinduced destruction. These phenomena are intimately linked to the generation, transformation, and deactivation of active sites. A comprehensive understanding of these light‐induced structural evolutions is indispensable for the rational design of high‐performance photocatalytic systems, but a holistic review synthesizing structural and active site transformations remains lacking. This review aims to bridge this gap by systematically summarizing recent research progress, including the impact of light on structure and catalytic sites throughout the lifecycle of photocatalysts, strategies for regulating structural evolution processes, related characterization and calculation methods. Finally, challenges and prospects in the research of photocatalysts are proposed, and some insights for improving photocatalytic efficiency and practical applications are provided. This review is the first to propose a unified framework linking photoexcitation, structural evolution, dynamic active sites and performance improvement, aiming to upgrade photocatalysis research from static material screening to dynamic system engineering.