Two eternal topics, sustainable energy and green environment drive the research of solar energy conversion and utilization to the forefront of science and technology. Herein, the hottest photocatalysts—metal–organic frameworks (MOFs) and their composites are highly focused on, and the comprehensive architecture strategies are extracted with a well-organized review of their infinite possibility in photocatalytic properties and performance. Further, the architecture strategies based on the track of photoelectrons during the photocatalytic process and the most key mention of the structure–function relationship are revealed with profundity perspective and easy-to-understand approach. So that, the great potential in pollutants degradation, water splitting for H 2 generation, and CO 2 reduction is successfully reviewed to promote the design of high-efficiency photocatalysts in the future. Finally, a systematic overview is made on the problems and challenges of MOF-based photocatalysts, and future development is prospected to point out the opportunities and directions.