Electrifying CO₂ Coupling With Small Molecules

Abstract Carbon capture and utilization (CCU) is pivotal for low‐carbon industry. Among varied techniques, coupling of carbon dioxide (CO 2 ) with small molecules to generate valuable‐added chemicals using renewable electricity stands out thanks to its cost‐effectiveness and sustainability. This review first highlights recent strategies in catalyst preparation for improving the efficiency and selectivity of electrochemical coupling reactions, including heterostructure catalysts, bimetallic catalysts, defect engineering, and coordination complexes. The progresses on mechanism investigation of C─N, C─O, and C─C coupling using in situ spectroscopies and online mass spectrometry are subsequently summarized. In addition, electrolyzer design and techno–economic analysis about process optimization and the integration of renewable energy are stressed. Finally, future challenges in catalyst optimization, reaction mechanism elucidation, and scale‐up implementation are discussed.