Hybridizing　two　heterocomponents　to　construct　a　built-in　electric　field　(BIEF)　at　the　interface　represents　a　significant　strategy　for　facilitating　charge　separation　in　carbon　dioxide　(CO2)-photoreduction.　However,　the　unidirectional　nature　of　BIEFs　formed　by　various　low-dimensional　materials　poses　challenges　in　adequately　segregating　the　photogenerated　carriers　produced　in　bulk.　In　this　study,　leveraging　zinc　oxide　(ZnO)　nanodisks,　a　sulfurization　reaction　is　employed　to　fabricate　Z-scheme　ZnO/zinc　sulfide　(ZnS)　heterojunctions　featuring　a　multiple-order　BIEF.　These　heterojunctions　reveal　distinctive　interfacial　structures　characterized　by　two　semicoherent　phase　boundaries.　The　cathodoluminescence　2D　maps　and　density　functional　theory　calculation　results　demonstrate　that　the　direction　of　the　multiple-order　BIEF　spans　from　ZnS　to　ZnO.　This　directional　alignment　significantly　fosters　the　spatial　separation　of　photogenerated　electrons　and　holes　within　ZnS　nanoparticles　and　enhances　CO2-to-carbon　monoxide　photoreduction　performance　(3811.7 µmol　h−1 g−1).　The　findings　present　a　novel　pathway　for　structurally　designing　BIEFs　within　heterojunctions,　while　providing　fresh　insights　into　the　migratory　behavior　of　photogenerated　carriers　across　interfaces.　©　2024　Wiley-VCH　GmbH.