A study explores the electrochemical synthesis of urea using nitrite and carbon dioxide on copper surfaces, revealing the critical role of electrode potential in reaction mechanisms and activity. The research combines a constant-potential method with an implicit solvent model to analyze reaction pathways and identify key intermediates, such as *CO-NH and *NH-CO-NH. The study demonstrates that urea synthesis activity increases with temperature, with Cu(100) showing the highest efficiency. The electric double-layer capacitance also plays a significant role in the reaction. The findings suggest two strategies to enhance urea synthesis efficiency: increasing the Cu(100) surface ratio and raising the reaction temperature. Urea is a vital nitrogen fertilizer, but traditional methods are energy-intensive and environmentally harmful. Electrochemical synthesis offers a greener alternative, though understanding the mechanism remains challenging. The study highlights the importance of electrode potential and the need for further research into reaction mechanism modulation. The results provide insights into the electrochemical urea synthesis process, emphasizing the role of potential, temperature, and surface properties in catalytic efficiency. The study also underscores the significance of the electric double-layer in influencing reaction kinetics. The research contributes to the development of more efficient and sustainable urea synthesis methods.A study explores the electrochemical synthesis of urea using nitrite and carbon dioxide on copper surfaces, revealing the critical role of electrode potential in reaction mechanisms and activity. The research combines a constant-potential method with an implicit solvent model to analyze reaction pathways and identify key intermediates, such as *CO-NH and *NH-CO-NH. The study demonstrates that urea synthesis activity increases with temperature, with Cu(100) showing the highest efficiency. The electric double-layer capacitance also plays a significant role in the reaction. The findings suggest two strategies to enhance urea synthesis efficiency: increasing the Cu(100) surface ratio and raising the reaction temperature. Urea is a vital nitrogen fertilizer, but traditional methods are energy-intensive and environmentally harmful. Electrochemical synthesis offers a greener alternative, though understanding the mechanism remains challenging. The study highlights the importance of electrode potential and the need for further research into reaction mechanism modulation. The results provide insights into the electrochemical urea synthesis process, emphasizing the role of potential, temperature, and surface properties in catalytic efficiency. The study also underscores the significance of the electric double-layer in influencing reaction kinetics. The research contributes to the development of more efficient and sustainable urea synthesis methods.