In‐Situ Probing CO Activation in Sulfur‐Enhanced Paired Electrocatalysis for CO ₂ ‐to‐C ₂₊ Conversion with Alcohol Oxidation

In a world striving for sustainable energy, advanced electrocatalysts are pivotal to enabling efficient chemical transformations with minimal energy costs. Herein, we uncover a practical approach for the simultaneous electrochemical CO₂ reduction (CO₂RR) and alcohol oxidation (AOR), enabling the selective valuable chemicals production. Central to this innovation is a self-supported electrocatalyst, featuring sulfur-enhanced CuBi₂O₄ nanospheres anchored on NrGO nanosheets (SCB/NG), achieved a faradaic efficiency for C₂₊ products (FE_C2+) exceeding 92.4% over 200 h, while demonstrating near-total selectivity for benzaldehyde and >83% for furfural. Beyond that, in situ Raman spectroscopy and DFT calculations reveal *CO dimerization and the key intermediates coverage, providing deep mechanistic insights into the reaction pathway. Additionally, by being integrated into a solar-powered platform, the bifunctional system achieves a solar-to-fuel conversion efficiency of 16% with over 98% retention, offering a scalable strategy for coupling CO₂ utilization with high-value chemical production and paving the way toward energy-efficient, carbon-neutral technologies.