Presented　herein　are　the　delicate　design　and　synthesis　of　S-scheme　NiTiO3　/CdS　heterostructures　composed　of　CdS　nanoparticles　anchored　on　the　surface　of　NiTiO3　nanorods　for　photocatalytic　CO2　reduction.　Systematic　physicochemical　studies　demonstrate　that　NiTiO3　/CdS　hybrid　empowers　superior　light　absorption　and　enhanced　CO2　capture　and　activation.　Electron　spin　resonance　validates　that　the　charge　carriers　in　NiTiO3　/CdS　follow　a　S-scheme　transfer　pathway,　which　powerfully　impedes　their　recombination　and　promotes　their　separation.　Importantly,　the　photogenerated　holes　on　CdS　are　effectively　consumed　at　the　hero-interface　by　the　electron　from　NiTiO3　,　preventing　the　photo-corrosion　of　the　metal　sulfide.　As　a　result,　with　Co(bpy)3　2　+　as　a　cocatalyst,　NiTiO3　/CdS　displays　a　considerable　performance　for　CO2　reduction,　affording　a　high　CO　yield　rate　of　20.8　mu　mol　h-1　.　Moreover,　the　photocatalyst　also　manifests　substantial　stability　and　good　reusability　for　repeated　CO2　reaction　cycles　in　the　created　tandem　photochemical　system.　In　addition,　the　possible　CO2　photoreduction　mechanism　is　constructed　on　the　basis　of　the　intermediates　monitored　by　in-situ　diffuse　reflectance　infrared　Fourier　transform　spectroscopy.　(c)　2025　Published　by　Elsevier　Ltd　on　behalf　of　The　editorial　office　of　Journal　of　Materials　Science　&　Technology.