Electrocatalytic urea synthesis is an emerging alternative technology to the traditional energy-intensive industrial urea synthesis protocol. Novel strategies are urgently needed to promote the electrocatalytic C–N coupling process and inhibit the side reactions. Here, we report a CuWO₄ catalyst with native bimetallic sites that achieves a high urea production rate (98.5 ± 3.2 μg h⁻¹ mg⁻¹_cat) for the co-reduction of CO₂ and NO₃⁻ with a high Faradaic efficiency (70.1 ± 2.4%) at −0.2 V versus the reversible hydrogen electrode. Mechanistic studies demonstrated that the combination of stable intermediates of *NO₂ and *CO increases the probability of C–N coupling and reduces the potential barrier, resulting in high Faradaic efficiency and low overpotential. This study provides a new perspective on achieving efficient urea electrosynthesis by stabilizing the key reaction intermediates, which may guide the design of other electrochemical systems for high-value C–N bond-containing chemicals.

电催化尿素合成是传统能源密集型工业尿素合成方案的新兴替代技术。迫切需要新的策略来促进电催化C-N偶联过程并抑制副反应。在这里，我们报道了一种具有天然双金属位点的 CuWO ₄催化剂，该催化剂可实现高尿素生产率（98.5 ± 3.2 μg h ^-1  mg ^-1 _{cat ），用于 CO 2}和 NO ₃ ^-的共还原，并具有高法拉第效率（ 70.1 ± 2.4%）（-0.2 V 时相对于可逆氢电极）。_{机理研究表明，稳定中间体*NO 2}和*CO的组合增加了C-N耦合的概率并降低了势垒，从而产生高法拉第效率和低过电势。这项研究为通过稳定关键反应中间体实现高效尿素电合成提供了新的视角，这可能会指导其他高价值含C-N键化学品的电化学系统的设计。