Z-Scheme　artificial　photosystems,　resembling　the　natural　photosynthesis　procedure,　circumvent　the　disadvantage　of　a　single-ingredient　photosystem　and　hold　fascinating　prospects　for　solar　energy　conversion.　Despite　the　advancements,　bottom-up　elaborate　design　of　composite　heterostructured　Z-scheme　photosystems　by　flexible　interface　engineering　for　photoredox　organic　transformation　has　been　poorly　investigated.　We　herein　report　the　construction　of　a　metal-based　Z-scheme　photoredox　systemviaa　progressive　self-assembly　strategy　integrated　with　a　facile　photo-deposition.　Tailor-made　hierarchically　branched　ligand-capped　Pd　nanocrystals　(NCs)　sandwiched　in-between　a　WO3nanorod　(NR)　core　and　CdS　shell　are　harnessed　as　the　charge　transport　modulator　to　regulate　the　interfacial　oxidation-reduction　kinetics　for　boosted　Z-scheme　photocatalysis.　The　intermediate　Pd　NCs　as　Schottky-type　electron　flow　mediators　considerably　accelerate　the　unidirectional　Z-scheme　charge　motion　rate,　endowing　multilayered　WO3@Pd@CdS　core-shell　heterostructures　with　significantly　boosted　net　efficiency　of　photoactivities　toward　anaerobic　selective　nitroaromatic　reduction　to　amino　derivatives　and　aromatic　alcohol　oxidation　to　aldehydes　under　visible　light　illumination.　The　predominant　active　species　produced　in　the　versatile　photocatalytic　selective　organic　transformation　were　explored　and　photocatalytic　mechanisms　were　thus　ascertained.　Our　endeavor　could　offer　a　promising　route　for　smartly　crafting　diverse　heterostructured　Z-scheme　photoredox　systems　for　solar　energy　conversion.　©　The　Royal　Society　of　Chemistry　2020.