Photocatalytic dehalogenation reduction, which converts a C–X bond into a C–H bond, plays a significant role in synthetic catalysis and pollutant remediation. However, the reduction is significantly affected by photoinduced electron transfer (PET) from organic photoredox catalysts to metal ions or clusters. By introducing photosensitive ligands and cluster-based nodes into metal–organic frameworks (MOFs), we synthesized Co₇(μ₃-O)₃-cluster MOFs using the easily redox cobalt ions and a tetraphenylbenzene-1,4-diamine-based ligand modified by the central skeleton, effectively regulating the redox potential. The synergistic interactions between the Co₇(μ₃-O)₃ cluster and the photosensitive ligands enable efficient PET process. This synergy provides a concise strategy for photocatalytic dehalogenation reduction using cobalt-cluster MOFs under mild conditions, which can be extended to aryl halide and halogenated aromatic pollutants.