In‐Situ Probing CO Activation in Sulfur‐Enhanced Paired Electrocatalysis for CO₂‐to‐C₂₊ 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 CO 2 reduction (CO 2 RR) and alcohol oxidation (AOR), enabling the selective valuable chemicals production. Central to this innovation is a self‐supported electrocatalyst, featuring sulfur‐enhanced CuBi 2 O 4 nanospheres anchored on NrGO nanosheets (SCB/NG), achieved a faradaic efficiency for C 2+ 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 CO 2 utilization with high‐value chemical production and paving the way toward energy‐efficient, carbon‐neutral technologies.