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Metal–organic frameworks (MOFs) represent a novel class of crystalline inorganic–organic hybrid materials with tunable semiconducting behavior. MOFs have potential for application in photocatalysis to produce sustainable solar fuels, owing to their unique structural advantages (such as clarity and modifiability) that can facilitate a deeper understanding of the structure–activity relationship in photocatalysis. This review takes the photocatalytic active sites as a particular perspective, summarizing the progress of MOF‐based photocatalysis for solar fuel production; mainly including three categories of solar‐chemical conversions, photocatalytic water splitting to hydrogen fuel, photocatalytic carbon dioxide reduction to hydrocarbon fuels, and photocatalytic nitrogen fixation to high‐energy fuel carriers such as ammonia. This review focuses on the types of active sites in MOF‐based photocatalysts and discusses their enhanced activity based on the well‐defined structure of MOFs, offering deep insights into MOF‐based photocatalysis. [ABSTRACT FROM AUTHOR]