Precisely　modulating　the　spatial　charge　migration/separation　constitutes　the　central　issue　in　dictating　the　solar　conversion　efficiency　of　photoelectrochemical　(PEC)　cells,　whereas　it　still　remains　a　grand　challenge.　Here,　we　conceptually　demonstrate　the　construction　of　hierarchically　ordered　metal　oxide　(MO)/transition-metal　chalcogenide　quantum　dots　(TMC　QDs)　multilayered　heterostructured　photoanodes,　that　is,　MO/[TMC　QDs(+)/TMC　QDs(-)]n　(TMC　QDs:　CdTe,　CdSe,　CdS),　by　a　simple　and　general　bottom-up　self-assembly　route.　Tailor-made　intrinsically　oppositely　charged　TMC　QDs　are　alternately　deposited　on　the　highly　ordered　MO　via　a　generic　ligand-triggered　electrostatic　interaction　to　craft　heterostructured　photoanodes.　The　charge-transfer　pathway　stimulated　by　the　photosensitization　of　TMC　QDs　is　finely　tuned　by　the　assembly　sequence.　The　advantageous　multilayered　nanoarchitecture　renders　the　MO/[TMC　QDs(+)/TMC　QDs(-)]n　photoanodes　exhibit　substantially　enhanced　PEC　performances　under　light　irradiation,　owing　to　the　applicable　energy-level　configuration　and　peculiar　combination　fashion　between　building　blocks　and　considerably　boosted　interfacial　charge　separation　resulting　from　generating　spatial　tandem　charge　transport.　Furthermore,　photosensitization　efficiency　comparison　among　TMC　QDs　is　comprehensively　performed　with　PEC　mechanisms　elucidated.　©