Abstract: In photo-assisted advanced oxidation processes, electrons in pollutants or catalysts are excited to higher energy levels under light irradiation. Subsequently, they release energy and return to the ground state. During this process, reactive oxygen species are generated, which drive the degradation and mineralization of pollutants. This review provides a comprehensive overview of three typical PAOPs: photo-excitation, photo-Fenton, and photocatalysis. Particular emphasis is placed on the detailed discussion of the mechanisms and technological advancements of photocatalysis-based pollutant degradation. Notably, metal-organic frameworks, composed of metal ion nodes and organic linkers, have garnered significant attention due to their unique properties, including high porosity, large specific surface area, flexible designability, and facile functionalization. Finally, the practical challenges hindering the real-world application of PAOPs are systematically summarized, providing critical insights for their industrialization and future development.