The　elaborate　development　of　photocatalysts　that　can　maximize　the　utility　of　solar　energy　with　simultaneous　photocatalytic　H-2　evolution　and　high-quality　chemicals　production　holds　great　promise　in　the　field　of　selective　photoredox　synthesis.　Herein,　the　in　situ　growth　of　CdS　nanowires　on　the　outside　surface　of　Co9S8　hollow　nanocages　is　reported　to　create　a　hierarchical　CdS/Co9S8　hollow　photocatalyst　for　efficient　photochemical　coupling　of　amines　to　produce　imines　and　H-2.　This　ingenious　hierarchical　photocatalyst　has　a　unique　hollow　structure　and　dense　interfacial　contact　with　a　type-I　band　orientation,　which　facilitates　the　interfacial　transfer　of　charge　carriers.　The　photocatalytic　activity　of　this　hierarchical　hollow　catalyst　is　significantly　enhanced　in　comparison　to　CdS　and　Co9S8,　and　distinctively　exhibits　excellent　recycling　stability.　Mechanistic　studies　have　shown　that　the　carbon-centered　radical　Ph((CH)-C-center　dot)NH2　is　essential　for　the　reaction.　Additionally,　the　CdS/Co9S8　hollow　hybrid　also　exhibits　outstanding　performance　in　coupling　various　primary　amines　to　the　corresponding　imines,　highlighting　the　broad　applicability　of　this　photocatalyst　for　C-N　coupling　reactions.　This　work　offers　a　new　strategy　for　the　efficient　design　of　heterostructured　hollow　semiconductor-based　photocatalysts　for　the　cooperative　coupling　of　clean　fuel　production　and　fine　chemical　synthesis.