Inorganic-organic　S-scheme　heterostructure　photocatalysts　have　demonstrated　exceptional　potential　in　boosting　charge　separation　for　CO2　reduction.　However,　the　reduction　typically　occurs　at　the　inorganic　site,　resulting　in　underutilization　of　high　CO2　adsorption　capacity　of　organic　material.　To　resolve　this　mismatch,　we　combined　a　low　conduction　band　iron　tungstate　(FeWO4)　with　a　dioxin-linked　covalent　organic　framework　(COF)　to　construct　S-scheme　heterojunction,　where　the　COF　serve　as　the　reduction　photocatalysts　and　FeWO4　act　as　the　oxidation　photocatalysts,　for　photocatalytic　CO2　reduction.　Density　functional　theory　(DFT)　calculations　and　in-situ　spectroscopic　analyses　confirm　that　the　FeWO4/COF　hybrids　steer　an　S-scheme　charge　transfer　pathway　driven　by　an　enhanced　internal　electric　field.　Benefiting　from　the　synergy　between　the　strong　CO2　adsorption　at　the　COF　cyano　site,　which　aligns　with　its　role　as　the　reduction　site,　and　the　unique　S-scheme　electron　transfer,　the　composites　achieve　a　significantly　higher　CO　yield　(55.9　μmol·g−1·h−1)　than　COF　(5.5　μmol·g−1·h−1)　with　100　%　selectivity　and　no　sacrificial　agents　or　sensitizers.　Isotope　tracer　experiments　verify　that　the　CO　was　from　CO2.　In-situ　Fourier　transform　infrared　spectroscopy　(FT-IR)　coupled　with　two-dimensional　correlation　spectroscopy　(2D-COS)　unveils　the　sequential　reduction　process　of　CO2.　This　study　envisions　a　harmoniously　aligned　inorganic/organic　S-scheme　heterojunction　for　boosting　CO2　photoreduction.　©　2025