Semiconductor-based　artificial　photoredox-catalyzed　organic　synthesis　offers　a　promising　and　green　opportunity　to　harness　solar　energy　for　green　organic　chemistry.　However,　the　precise　manipulation　of　product　selectivity　over　semiconductor-based　photocatalysts　for　selective　organic　synthesis　remains　challenging.　In　this　work,　we　report　the　rational　preparation　and　application　of　two　kinds　of　cocatalyst,　(RuS2　or　Cu2S)-decorated　monolayer　ZnIn2S4,　for　the　selective　dehydrocoupling　of　aromatic　amines　into　tunable　C　N　coupled　imines　or　C-N　coupled　secondary　amines,　respectively,　under　visible　light　irradiation.　The　presence　of　the　RuS2　or　Cu2S　cocatalyst　not　only　facilitates　the　charge　carrier　separation　and　migration　owing　to　the　well-matched　energy　band　structure,　but　also　maneuvers　the　interfacial　charge　transfer　routes　for　the　selectivity　switching　between　C　N　and　C-N　product　formation.　This　work　would　inspire　the　rational　design　of　ingenious　semiconductor-based　composites　toward　selective　modulation　in　heterogeneous　photocatalytic　organic　synthesis.　©　2023　The　Royal　Society　of　Chemistry.