Finely　tuning　the　charge　transfer　constitutes　a　central　challenge　in　photocatalysis,　yet　exquisite　control　of　the　directional　charge　transfer　to　the　target　reactive　sites　is　hindered　by　the　rapid　charge　recombination.　Herein,　dual　separated　charge　transport　channels　were　fabricated　in　a　one-dimensional　transition-metal　chalcogenide　(TMC)-based　system　via　an　elaborate　layer-by-layer　(LbL)　self-assembly　approach,　for　which　oppositely　charged　metal-ion-coordinated　branched　polyethylenimine　(BPEI)　and　MoS2　quantum　dots　(QDs)　were　alternately　integrated　to　fabricate　the　multilayered　TMC@(BPEI/MoS2　QDs)n　heterostructures　with　controllable　interfaces.　Photocatalytic　hydrogen　generation　performances　of　such　ternary　heterostructures　under　visible　light　irradiation　were　evaluated,　which　unravels　that　the　BPEI　layer　not　only　behaves　as　＂molecule　glue＂　to　enable　the　electrostatic　LbL　assembly　with　MoS2　QDs　in　an　alternate　stacking　fashion　on　the　TMC　frameworks　but　also　acts　as　a　unidirectional　hole-transfer　channel.　More　significantly,　transition-metal　ions　(Fe2+,　Co2+,　Ni2+,　Cu2+,　and　Zn2+)　coordinated　on　the　outmost　BPEI　layer　are　able　to　function　as　interfacial　electron　transfer　mediators　for　accelerating　the　interfacial　cascade　electron　transport　efficiency.　These　simultaneously　constructed　dual　high-speed　electron　and　hole-transfer　channels　are　beneficial　for　boosting　the　charge　separation　and　enhancing　the　photocatalytic　hydrogen　evolution　performances.　Copyright　©　2020　American　Chemical　Society.