Achieving　a　precise　understanding　and　accurate　design　of　heterogeneous　catalysts　based　on　bioinspired　principles　is　challenging　yet　crucial　to　digging　out　optimal　materials　for　artificial　catalysis.　Here,　an　ADH-mimicking　dual-site　photocatalyst　(YCuCdS)　is　developed,　and　demonstrates　the　powerful　effects　of　atomic　site　configuration　and　proton　transfer　environments　on　alcohol-amine　coupling.　Mechanism　studies　reveal　that　the　alcohol　substrate　is　effectively　dehydrogenated　at　the　Y　sites,　forming　the　carbonyl　intermediates　that　rapidly　experience　condensation　with　the　amine.　Meanwhile,　the　released　hydrogen　species　(H-ads)　migrate　from　adjacent　Cu　sites　to　active　S　atoms,　promoting　H-2　production　and　hindering　the　over-hydrogenation　of　imine.　As　a　result,　a　high　imine　yield　of　92%　is　achieved,　along　with　an　H-2　production　rate　of　7400　mu　mol　g(-1)　h(-1).　This　work　showcases　an　effective　strategy　for　the　design　of　heterogeneous　catalysts　with　bioinspiration.