Magic-sized　nanoclusters　(MSCs)　have　recently　deemed　as　a　novel　and　crucial　sector　of　nanomaterials　on　account　of　their　large　absorption　coefficient　for　light　harvesting,　peculiar　quantum　confinement　effect,　and　abundant　active.　Nevertheless,　precise　control　of　photoinduced　charge　carriers　over　MSCs　has　so　far　not　yet　been　reported　because　of　the　ultra-short　carrier　lifetime　and　intrinsic　instability　of　MSCs,　which　renders　the　complexity　of　MSCs　photosystems　with　photoredox　mechanism　remaining　blank.　Herein,　we　for　the　first　time　conceptually　demonstrate　the　grafting　of　amino-containing　organic　molecular　onto　the　L-cysteine　(L-Cys)　ligand　of　CdSe@L-Cys　MSCs　as　charge　transport　mediator,　and　the　amino　functional　group　acts　as　an　efficient　electron-withdrawing　trap,　which　markedly　boosts　the　charge　separation　and　prolongs　the　charge　lifetime　of　CdSe@L-Cys　MSCs,　resulting　in　the　significantly　improved　photocatalytic　hydrogen　generation　performances　under　visible　light　irradiation　along　with　favorable　stability.　Our　work　will　provide　sparking　ideas　for　fine　tuning　of　photoinduced　charge　separation　and　transfer　over　transition　metal　chalcogenides　MSCs　photosystems　for　solar-to-hydrogen　energy　conversion.　©　2024　Elsevier　Inc.