Interfacial　charge　separation　and　transfer　enduringly　constitutes　a　core　issue,　which　dictates　the　efficiency　of　a　photocatalytic　reaction.　However,　the　exquisite　modulation　of　directional　charge　transfer　to　ideal　reaction　sites　remains　challenging　in　terms　of　the　fast　recombination　rates　of　photoinduced　charge　carriers　and　the　difficulty　in　constructing　spatially　separated　high-speed　charge　transfer　channels.　Herein,　we　demonstrate　the　general　construction　of　metal/metal　chalcogenide　heterostructures　by　a　facile,　green,　universal,　scalable　and　simple　yet　efficient　electrostatic　self-assembly　strategy,　wherein　tailor-made　positively　charged　4-dimethylaminopyridine　(DMAP)-capped　metal　nanocrystals　(NCs,　Au,　Pd)　were　spontaneously　and　intimately　tethered　on　negatively　charged　one-dimensional　(1D)　transition　metal　chalcogenides　(TMC:　CdS,　CdIn2S4,　ZnIn2S4,　and　Zn0.5Cd0.5S)　initiated　by　a　surface　linker　(DMAP)　to　fabricate　well-defined　heterostructured　photocatalysts.　Moreover,　the　interface　configurations　between　the　metal　NCs　and　TMC　matrices　were　finely　designed　by　ligand　engineering　to　afford　controllable　charge　transfer　pathways.　Intriguingly,　this　tunable　charge　flow　endows　the　metal　NC/TMC　heterostructures　with　markedly　enhanced　and　versatile　photoredox　performance　toward　the　anaerobic-selective　photoreduction　of　aromatic　nitro　compounds,　photocatalytic　hydrogen　generation,　and　photocatalytic　selective　oxidation　of　aromatic　alcohols　under　visible　light　irradiation,　in　which　metal　NCs　play　imperative　roles　in　efficiently　capturing　Schottky-junction-driven　electrons　from　the　TMC　substrates　without　the　interference　of　the　hierarchically　branched　ligand　capped　on　the　metal　NCs.　Our　studysheds　light　on　the　rational　modulation　of　interfacial　charge　flow　in　photoredox　catalysis　for　substantial　solar　energy　conversion.　©　2019　The　Royal　Society　of　Chemistry.