AbstractElectrosynthesis of urea from CO₂ and NO_X provides an exceptional opportunity for human society, given the increasingly available renewable energy. Urea electrosynthesis is challenging. In order to raise the overall electrosynthesis efficiency, the most critical reaction step for such electrosynthesis, C-N coupling, needs to be significantly improved. The C-N coupling can only happen at a narrow potential window, generally in the low overpotential region, and a fundamental understanding of the C-N coupling is needed for further development of this strategy. In this regard, we perform ab initio Molecular Dynamics simulations to reveal the origin of C-N coupling under a small electrode potential window with both the dynamic nature of water as a solvent, and the electrode potentials considered. We explore the key reaction networks for urea formation on Cu(100) surface in neutral electrolytes. Our work shows excellent agreement with experimentally observed selectivity under different potentials on the Cu electrode. We discover that the ^*NH and ^*CO are the key precursors for C-N bonds formation at low overpotential, while at high overpotential the C-N coupling occurs between adsorbed ^*NH and solvated CO. These insights provide vital information for future spectroscopic measurements and enable us to design new electrochemical systems for more value-added chemicals.