Abstract Electrochemical CO 2 reduction has been recognized as a promising solution in tackling energy‐ and environment‐related challenges of human society. In the past few years, the rapid development of advanced electrocatalysts has significantly improved the efficiency of this reaction and accelerated the practical applications of this technology. Herein, representative catalyst structures and composition engineering strategies in regulating the CO 2 reduction selectivity and activity toward various products including carbon monoxide, formate, methane, methanol, ethylene, and ethanol are summarized. An overview of in situ/operando characterizations and advanced computational modeling in deepening the understanding of the reaction mechanisms and accelerating catalyst design are also provided. To conclude, future challenges and opportunities in this research field are discussed.