Xingqun Li, Junjie Yuan, Zhongqiu Wu, Han Zhang, Yong Li, Quan Zhang, Hui Xu
The electrocatalytic CO 2 reduction reaction (CO 2 RR) offers a sustainable pathway to convert CO 2 into value‐added chemicals. However, a systematic categorization of the resulting chemical products, along with comprehensive strategies toward high efficiency and selectivity of CO 2 RR has yet to be fully established. Herein, this review systematically summarizes recent advances in CO 2 RR, covering products from C 1 compounds to C 2+ chemicals generated via C–C coupling. Subsequently, special emphasis is placed on steering post‐coupling pathways to selectively produce ethylene or ethanol, as well as mechanisms for carbon‐chain extension toward C 3 products like n‐propanol. Moreover, multifactor strategies to enhance CO 2 RR efficiency, including suppressing hydrogen evolution, rational catalyst design, electrolyte microenvironment modulation, and flow cell reactor integration are dissected. Finally, key scientific challenges and techno‐economic barriers of this carbon‐neutral technology are highlighted.