Atomic‐scale Mott‐Schottky Analogy in SnCu Nanoalloy Promote High‐Efficiency Urea Electrosynthesis at Ultralow Potential

Electrocatalytic urea synthesis from CO2 and NO3‐ offers a sustainable strategy to address environmental challenges and growing urea demand. However, current systems suffer inefficient C‐N coupling due to poor selectivity toward critical C/N‐intermediates. Herein, we engineered atomic‐scale Mott‐Schottky analogy in SnCu nanoalloy to create electron‐enriched Cu sites, enabling remarkable urea production through quadruple synergy. Sn2Cu delivered exceptional urea yield (28.9 mmol h‐1 gcat.‐1) with 46.7% Faradaic efficiency (FE) in H‐cell, while demonstrating practical potential with superior catalytic performance (yield: 72.6 mmol h‐1 gcat.‐1, FE: 41.3%, stability: 60 hours) at ‐0.52 V in flow cell. In‐situ synchrotron radiation Fourier transform infrared spectroscopy and theoretical calculations revealed electron‐enriched Cu active sites enhanced CO2/NO3‐ co‐adsorption and *CO coverage, while steering reaction pathway toward *CO‐*NHO coupling and suppressing hydrogen evolution, thereby reducing rate‐determining step energy barrier and prioritizing C‐N coupling. This work develops a structure‐adsorption‐reactivity framework, providing fundamental guidance for advanced urea electrocatalyst design.