Key Strategies for Electrocatalytic C‐N Coupling: From Reaction Pathways to Catalyst Engineering and Performance Evaluation

ABSTRACT The construction of C‐N bonds is of fundamental importance in organic synthesis, pharmaceutical chemistry, agrochemical science, and functional materials, serving as a key structural unit in numerous bioactive molecules and functional compounds. Electrocatalytic C‐N coupling has attracted considerable interest due to its environmentally friendly nature and mild reaction conditions. By utilizing renewable energy to drive the transformation, this strategy enables efficient and controllable formation of C‐N bonds. A comprehensive overview of reaction mechanisms, engineering strategies and performance evaluation systems is urgently needed to deepen the understanding of structure‐activity relationships and provide clear guidance for future research directions. Accordingly, this review systematically summarizes recent advances in electrocatalytic C‐N coupling mainly from three main aspects: (1) elucidating the activation mechanisms and representative reaction pathways of various carbon sources and nitrogen sources; (2) discussing rational catalyst design strategies, including the modulation of active sites and the optimization of local microenvironment; and (3) summarizing the existing evaluation methodologies and technical means. Finally, through the in‐depth discussion of current challenges and future development directions, this review aims to offer theoretical foundations and technical support for practical applications of electrocatalytic C‐N coupling, promoting the construction of more efficient and sustainable processing systems.