Light-driven　valorization　conversion　of　CO2　is　an　encouraging　carbon-negative　pathway　that　shifts　energy-reliance　from　fossil　fuels　to　renewables.　Herein,　a　hierarchical　urchin-like　hollow-TiO2@CdS/ZnS　(HTO@CdS/ZnS)　Z-scheme　hybrid　synthesized　by　an　in　situ　self-assembly　strategy　presents　superior　photocatalytic　CO2-to-CO　activity　with　nearly　100%　selectivity.　Specifically,　benefitting　from　the　reasonable　architectural　and　interface　design,　as　well　as　surface　modification,　this　benchmarked　visible-light-driven　photocatalyst　achieves　a　CO　output　of　62.2　μmol·h-1　and　a　record　apparent　quantum　yield　of　6.54%　with　the　Co(bpy)32+　(bpy　=　2,2′-bipyridine)　cocatalyst.　It　rivals　all　the　incumbent　selective　photocatalytic　conversion　of　CO2　to　CO　in　the　CH3CN/H2O/TEOA　reaction　systems.　Specifically,　the　addition　of　HTO　and　stabilized　ZnS　enables　the　photocatalyst　to　effectively　upgrade　optical　and　electrical　performances,　contributing　to　efficient　light-harvesting　and　photogenerated　carrier　separation,　as　well　as　interfacial　charge　transfer.　The　tremendous　enhancement　of　photocatalytic　performance　reveals　the　superiority　of　the　Z-scheme　heterojunction　assembled　from　HTO　and　CdS/ZnS,　featuring　the　inner　electric　field　derived　from　the　band　bending　of　HTO@CdS/ZnS　make　CdS　resistant　to　photocorrosion.　This　study　allows　access　to　inspire　studies　on　rationally　modeling　and　constructing　diverse　heterostructures　for　the　storage　and　conversion　of　renewables　and　chemicals.　©　2023　American　Chemical　Society.