Tailoring O‐Monodentate Adsorption of CO2 Initiates C–N Coupling for Efficient Urea Electrosynthesis with Ultrahigh Carbon Atom Economy

The thermodynamically and kinetically sluggish electrocatalytic C–N coupling from CO2 and NO3− is inert to initially take place while typically occurring after CO2 protonation, which severely dwindles urea efficiency and carbon atom economy. Herein, we report a single O‐philic adsorption strategy to facilitate initial C–N coupling of *OCO and subsequent protonation over dual‐metal hetero‐single‐atoms in N2–Fe–(N–B)2–Cu–N2 coordination mode (FeN4/B2CuN2@NC), which greatly inhibits the formation of C‐containing byproducts and facilitates urea electrosynthesis in an unprecedented C‐selectivity of 97.1% with urea yield of 2072.5 μg h−1 mgcat.−1 and 71.9% faradaic efficiency, outperforming state‐of‐the‐art electrodes. The carbon‐directed antibonding interaction with Cu–B is elaborated to benefit single O‐philic adsorption of CO2 rather than conventional C‐end or bridging O,O‐end adsorption modes, which can accelerate the kinetics of initiated C–N coupling and protonation. Theoretical results indicate that the O‐ monodentate adsorption pathway benefits the thermodynamics of the C–N coupling of *OCO with *NO2 and the protonation rate‐determining step, which markedly inhibits CO2 direct protonation. This oriented strategy of manipulating reactant adsorption patterns to initiate a specific step is universal to moderate oxophilic transition metals and offers a kinetic‐enhanced path for multiple conversion processes.