CO2　reduction　to　carbon　feedstocks　using　heterogeneous　photocatalysis　technique　has　been　deemed　as　an　attractive　means　of　addressing　both　deteriorating　greenhouse　effect　and　depletion　of　fossil　fuels.　Nevertheless,　deficiency　of　accessible　active　sites　on　the　catalyst　surface,　low　CO2　adsorption　rate,　and　short　carrier　lifetime　retard　the　photocatalytic　CO2　conversion　into　hydrocarbon　fuels.　In　this　work,　the　controllable　construction　of　spatially　separated　directional　charge　transport　pathways　over　multilayered　heterostructured　transition　metal　chalcogenides　(TMCs)　based　photosystems　for　high-performance　photocatalytic　CO2-to-syngas　conversion　are　shown.　In　this　scenario,　ultrathin　non-conjugated　insulating　poly(diallyl-dimethyl-ammonium　chloride)　(PDDA)　layer　are　intercalated　in-between　TMCs　and　layered　double　hydroxide　(LDH)　and　serve　as　an　efficient　electron　transfer　mediator,　whilst　LDH　functions　as　a　hole-withdrawing　regulator,　both　of　which　synergistically　foster　the　spatial　vectorial　charge　migration/separation　over　TMCs,　thus　endowing　the　TMCs/PDDA/LDH　heterostructures　with　significantly　boosted　visible-light-driven　photoactivity　toward　CO2　conversion　into　syngas.　This　work　can　inspire　sparkling　new　ideas　to　realize　fine　tuning　of　charge　motion　for　stimulating　solar-to-fuel　conversion.