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Electrochemical C–N coupling via the coreduction of CO₂and nitrogenous species (N₂/NO_x) presents a sustainable route to synthesize value‐added C–N compounds under mild conditions. However, competing pathways and mismatched intermediate kinetics hinder the selective formation of products like urea, amines, and amides. Recent advances reveal that rational modulation of the electrochemical microenvironment can effectively steer reaction pathways and stabilize coupling‐relevant intermediates. This review systematically summarizes how microenvironment engineering, originally developed for CO₂and NO_xreduction reactions, can be leveraged to enhance C–N coupling efficiency and selectivity. The key strategies are categorized into 1) catalyst‐centered design (e.g., ligand coordination, defect engineering, and morphology control), 2) ionic and electrolyte modifications (e.g., cation/pH effects), and 3) dynamic approaches such as pulsed electrolysis. These methods shape local fields, surface coverage, and mass transport properties, ultimately directing reactants toward cross‐coupling over competing routes. By drawing parallels with well‐established CO₂RR/NO_xRR systems and showcasing emerging examples in C–N coupling, the central role of microenvironment control is highlighted. Finally, a perspectives on strategies to further improve activity, selectivity, and atom economy in future C–N coupling systems are offered. 

Transition-metal ions regularly undergo charge transfer (CT) by directly interacting with electrodes, and this CT governs the performance of devices for numerous applications like energy storage and catalysis. These CT reactions are deemed inner sphere because they involve direct formation of a chemical bond between the electrode and the metal ion. Predicting inner-sphere CT kinetics on electrodes using simple physicochemical descriptors would aid the design of electrochemical systems with improved kinetics. Herein, we report that the average energy of the d electrons (i.e., d-band center) of a transition-metal electrode rationalizes the kinetic trends of inner-sphere CT of transition-metal ions. We demonstrate that V2+/V3+, an important redox reaction for flow batteries, is an inner-sphere reaction and that the kinetic parameters correlate with the adsorption strength of the vanadium intermediate on Au, Ag, Cu, Bi, and W electrodes, with W being the most active electrode reported to date. We show that the adsorption strength of the vanadium intermediate linearly correlates with the d-band center such that the d-band center serves as a simple descriptor for the V2+/V3+ kinetics. We extract kinetic data from the literature for four other inner-sphere CT reactions of metal ions involving Cr-, Fe-, and Co-based complexes to show that the d-band center also linearly correlates with kinetic trends for these systems. The d-band center of the electrode is a general descriptor for heterogeneous inner-sphere CT because it correlates with the adsorption strength of the metal-ion intermediate. The d-band center descriptor is analogous to the d-electron configuration of metal ions serving as a descriptor for homogeneous inner-sphere CT because the d-electron configuration controls bond strengths of intermediate metal-ion complexes.