Description:
<jats:sec><jats:label /><jats:p>Converting CO<jats:sub>2</jats:sub> into valuable chemical products has been intensively explored in recent years. Benefited from the substantial cost reduction of clean electricity, the electrochemical methods have been emerging as a potential means for CO<jats:sub>2</jats:sub> conversion and fixation. Direct electrochemical CO<jats:sub>2</jats:sub> reduction reaction (CO<jats:sub>2</jats:sub>RR) with H<jats:sub>2</jats:sub>O is achieved with continuously improved efficiency, selectivity and stability. In contrast, the coupled CO<jats:sub>2</jats:sub>RR with small molecules and organic substrates, which can allow to form higher valuable chemicals, is still hindered by the poor selectivity, unclear reaction mechanisms, and suboptimal performances of electrocatalysts. Herein, the development of CO<jats:sub>2</jats:sub>RR with electrocatalysts and reaction mechanisms is first introduced. Several representative examples are described for emphasizing concepts and methodologies. The research process and reaction mechanisms of the coupled CO<jats:sub>2</jats:sub>RR are then briefly discussed. Finally, challenges and perspectives in this field are addressed to further inspire the development of the fundamental understanding of reaction mechanisms for coupled CO<jats:sub>2</jats:sub>RR, as well as the optimization of electrocatalysts, electrolytes, and electrolyzers with high activity and selectivity.</jats:p></jats:sec>