Photocatalytic　hydrogen　(H2)　production　coupled　with　selective　oxidation　of　organic　compounds　into　high-value-added　organic　intermediates　has　expansive　prospects　in　the　utilization　and　transformation　of　solar　energy,　which　meets　the　development　requirements　of　green　chemistry.　In　this　work,　high-efficiency　hole　cocatalyst　PdS-decorated　In2S3　flower-like　microspheres　are　fabricated　for　the　effective　visible-light-driven　C-N　coupling　of　amines　to　imines　coupled　with　H2　evolution.　Owing　to　the　establishment　of　the　internal　electric　field,　which　further　boosts　the　transfer　of　photoexcited　holes　to　PdS,　PdS-In2S3　exhibits　distinctly　enhanced　photocatalytic　redox　performance,　which　is　39.8　times　higher　for　H2　and　14.3　times　higher　for　N-benzylidenebenzylamine　than　that　of　the　blank　In2S3,　along　with　high　selectivity　and　stability.　Furthermore,　the　practicability　of　dehydrogenation　coupling　of　various　aromatic　amines　to　the　corresponding　C-N　coupling　products　on　PdS-In2S3　has　been　demonstrated　and　a　plausible　reaction　mechanism　has　been　proposed.　This　work　is　anticipated　to　stimulate　further　interest　in　establishing　an　innovative　photoredox　platform　for　selective　organic　synthesis　coupled　with　H2　evolution　in　a　green　and　sustainable　way.　Keywords:　In2S3;　Photoredox　dual　reaction;　Hydrogen　evolution;　Visible　light;　Hole　cocatalyst.　©　2024　RSC.