Photocatalytic technology has received increasing attention in recent years. A pivotal facet of photocatalytic technology lies in the development of photocatalysts. Porous metal–organic framework (MOF) materials, distinguished by their unique properties and structural characteristics, have emerged as a focal point of research in the field, finding widespread application in the photo-treatment and conversion of various substances. Fe-based MOFs have attained particular prominence. This review explores recent advances in the photocatalytic degradation of aqueous and gaseous substances. Furthermore, it delves into the interaction between the active sites of Fe-MOFs and pollutants, offering deeper insights into their mechanism of action. Fe-MOFs, as photocatalysts, predominantly facilitate pollutant removal through redox processes, interaction with acid sites, the formation of complexes with composite metal elements, binding to unsaturated metal ligands (CUSs), and hydrogen bonding to modulate their respiratory behavior. This review also highlights the focal points of future research, elucidating the challenges and opportunities that lie ahead in harnessing the characteristics and advantages of Fe-MOF composite catalysts. In essence, this review provides a comprehensive summary of research progress on Fe-MOF-based catalysts, aiming to serve as a guiding reference for other catalytic processes.