Visible-light-driven　semiconductor-catalyzed　CO2　conversion　into　valuable　chemicals　and　industrial　feedstocks　is　one　of　the　superior　pathways　to　address　the　excess　carbon　emissions　and　energy　shortages.　Herein,　an　innovative　step-scheme　(S-scheme)　heterojunction　assembled　from　bulk　CdLa2S4　and　surface　rare-earth　perovskite-type　oxide　LaNiO3　with　precisely　engineered　suitable　band　alignment　is　employed　for　the　selective　photocatalytic　conversion　of　CO2　to　CO.　The　optimized　8%-LaNiO3/CdLa2S4　photocatalyst　exhibits　an　outstanding　CO　output　of　up　to　102.43　μmol　h-1　with　a　selectivity　of　about　83.4%,　rivaling　all　of　the　similar　incumbent　photocatalytic　reaction　systems　for　CO2-to-CO　conversion.　It　highlights　the　effectiveness　of　the　S-scheme　heterojunction　LaNiO3/CdLa2S4　in　hindering　the　recombination　of　the　photogenerated　electron-hole　pairs.　Meanwhile,　a　remarkable　apparent　quantum　efficiency　(AQE)　of　as　high　as　6.76%　is　achieved,　as　well　as　the　CO　output　is　still　maintained　at　99.5%　of　the　initial　value　after　five　cycle　tests,　revealing　the　superior　repeatability　and　reliability　of　the　8%-LaNiO3/CdLa2S4　photocatalyst　for　solar-to-chemical　conversion.　In　addition,　an　experimentally　verified　band　alignment-boosted　reaction　mechanism　is　proposed.　This　study　highlights　the　construction　of　structurally　flexible　and　highly　designable　S-scheme　heterojunctions,　demonstrating　potential　application　in　carbon-negative　energy　conversion.　©　2023　American　Chemical　Society