Atomically　precise　metal　nanoclusters　(NCs)　represent　an　emerging　sector　of　light-harvesting　antennas　by　virtue　of　peculiar　atomic　stacking　fashion,　quantum　confinement　effect,　and　molecular-like　discrete　energy　band　structure.　Nevertheless,　precise　control　of　charge　carriers　over　metal　NCs　has　yet　to　be　achieved　by　the　short　carrier　lifetime　and　intrinsic　instability　of　metal　NCs,　which　renders　the　complexity　of　metal　NCs-based　photosystems　with　photoredox　mechanisms　remaining　elusive.　Herein,　fine　tuning　of　charge　migration　over　metal　NCs　is　demonstrated　by　constructing　directional　charge　transfer　channels　in　multilayered　heterostructure　enabled　by　a　facile　layer-by-layer　(LbL)　assembly　approach,　wherein　oppositely　charged　branched　poly-ethylenimine　(BPEI)　and　glutathione　(GSH)-capped　gold　NCs　[Au-x　NCs,　Au-25(GSH)(18)　NCs]　are　alternately　deposited　on　the　metal　oxide　(MOs:　TiO2,　WO3,　Fe2O3)　substrates.　TheAu(x)　(Au-25)　NCs　layer　serves　as　light-harvesting　antennas　for　engendering　charge　carriers,　andBPEI　interim　layer　uniformly　intercalated　at　the　interface　of　Au-x　NCs　layer　constitutes　the　tandem　hole　transport　channel　for　motivating　the　charge　transfer　cascade,　resulting　in　the　considerably　enhanced　photoelectrochemical　water　oxidation　performances.　Besides,　poor　photo-stability　of　Au-x　NCs　is　surmounted　by　stimulating　the　hole　transfer　kinetics　process.