Modulation　of　photoinduced　charge　separation/migration　and　construction　of　controllable　charge　transfer　pathway　over　photoelectrodes　have　been　attracting　enduring　interest　in　semiconductor-based　photoelectrochemical　(PEC)　cells　but　suffer　from　sluggish　charge　transport　kinetics.　Here,　we　report　a　general　approach　to　fabricate　NP-TNTAs/(TMCs　QDs/PSS)(n)　(X　=　Te,　Se,　s)　photoanodes　via　a　facile　and　green　electrostatic　layer-by-layer　(LbL)　self-assembly　strategy,　for　which　transition-metal　chalcogenides　quantum　dots　(TMCs　QDs)　[CdX　(X　=　Se,　Te,　S)]　and　poly(sodium　4-styrenesulfonate)　(PSS)　were　periodically　deposited　on　the　nanoporous　TiO2　nanotube　arrays　(NP-TNTAs)　via　substantial　electrostatic　force,　resulting　in　the　continuous　charge　transfer　pathway.　NP-TNTAs/(TMCs　QDs/PSS)(n)　photoanodes　demonstrate　significantly　enhanced　solar-driven　photoelectrochemical　(PEC)　water　oxidation　activities,　relative　to　NP-TNTAs　and　TMCs　QDs　under　visible　and　simulated　sunlight　irradiation,　predominantly　because　of　the　suitable　energy　level　configuration　between　NP-TNTAs　and　TMCs　QDs,　unique　integration　mode,　and　high-speed　interfacial　charge　separation　rate　endowed　by　LbL　assembly.　The　ultrathin　PSS　intermediate　layer　functions　as　＂molecule　glue＂　for　pinpoint　and　uniform　self-assembly　of　TMCs　QDs　on　the　framework　of　NP-TNTAs　and　photosensitization　effect　of　TMCs　QDs　triggers　the　unidirectional　charge　transfer　cascade,　synergistically　boosting　the　charge　separation/transfer　efficiency.　Our　work　offers　an　efficacious　approach　to　craft　multilayered　photoelectrodes　and　spur　further　interest　in　finely　tuning　the　spatial　charge　flow　in　PEC　cell　for　solar-to-hydrogen　conversion.