Halogenated　organic　compounds　are　a　kind　of　common　environmental　pollutants.　Photocatalytic　dehalogenation　of　C-halogen　(C-X)　bonds　to　C-H　bonds　can　not　only　control　environmental　pollution　but　also　realize　important　organic　conversion　reactions.　However,　the　electron　transfer　kinetics　of　photocatalytic　reduction　of　the　C-X　bond　for　semiconductor/MOF　composites　has　remained　unexplored.　Herein,　we　successfully　synthesized　CdS/Zn(impim)　(MOF)　dots-on-rods　composite　photocatalyst　under　mild　conditions.　Zn(impim)　MOF　consists　of　Zn(μ-N)4　clusters　and　imidazole　derivative　ligands.　Zn(impim),　as　a　carrier,　is　beneficial　to　the　dispersion　of　CdS　nanoparticles　and　avoiding　the　agglomeration　of　CdS　nanoparticles.　The　photocatalytic　performance　of　CdS/Zn(impim)　composites　for　the　reduction　of　the　C-X　bond　is　much　higher　than　that　of　pure　CdS　or　Zn(impim).　This　high　activity　is　due　to　the　high　electron　separation　efficiency　of　CdS　assisted　by　Zn(impim).　Under　visible　light　irradiation,　Zn(impim)　is　not　excited　due　to　its　wide　band　gap　of　3.26　eV.　Through　metal-to-ligand　charge　transfer　of　Zn(μ-N)4　clusters,　Zn(impim)　accepts　excited　electrons　from　CdS　because　the　Fermi　energy　level　of　CdS　is　more　negative　by　Kelvin　probe　force　microscopy.　Moreover,　fluorescence　spectrum　and　femtosecond　transient　absorption　spectroscopy　reveal　the　related　electron　transfer　kinetics　in　detail.　In　addition,　the　inherent　porous　structure　of　MOFs　is　beneficial　to　the　adsorption　of　halogenated　hydrocarbons,　providing　a　suitable　environment　for　the　dehalogenation　reaction,　thus　improving　the　activity.　This　work　can　further　understand　the　electron　transfer　mechanism　in　semiconductor/MOF　composites　for　photocatalytic　halide　dehalogenation.　©　2023　American　Chemical　Society