In summary, this work pioneers a solar-driven tandem strategy that integrates S-scheme photocatalysis with industrial carbonylation under ambient conditions, enabling direct conversion of CO₂ to value-added amides. The breakthrough manifests in three aspects: First, the S-scheme charge transfer mechanism in CeO₂/Bi₂S₃ photocatalysts verified by in situ irradiated XPS, DFT calculations, EPR radical trapping, and fs-TA measurements resolves the inherent conflict between carrier separation and thermodynamic capability while preserving strong redox potentials. This achieves high CO production activity and selectivity (14.05 mmol g^–1, 98%). Second, the innovative tandem carbonylation design employs a gas-diffusion-interconnected two-chamber reactor, enabling in situ utilization of photogenerated CO for quantitative conversion to pharmaceutical amides via Pd-catalyzed carbonylation, eliminating CO storage risks. Finally, operating at room temperature under solar irradiation, this approach transforms greenhouse gas CO₂ into high-value chemicals (e.g., drug intermediates), marking a significant stride toward sustainable artificial carbon cycling.