<p>Electrosynthesis of urea at practical relevant current densities remains challenging due to competing side reactions, particularly at the elevated overpotentials required to sustain high currents. Here we propose a catalyst design strategy for selective urea production at practical current densities, emphasizing materials with low activity for competing CO₂ reduction and hydrogen evolution, and high activity for nitrate activation under high overpotentials. We develop a cadmium-modified Fe₂O₃ (Cd–Fe₂O₃) catalyst composite, achieving a high urea partial current density of approximately 140 mA cm⁻² at a modest cathodic potential of −0.5 V versus reversible hydrogen electrode, with an appreciable Faradaic efficiency of 52%. Through detailed kinetics analysis, in situ spectroscopic investigations and density functional theory calculations, we reveal that Cd incorporation into Fe₂O₃ substantially weakens *CO adsorption by altering the electronic structure and preserving oxidized Fe species. This modification suppresses undesired Volmer-type hydrogen adsorption while promoting *CO₂NH₂ intermediate protonation, enhancing urea formation. As a result, competing hydrogen evolution is effectively suppressed, and high urea selectivity is maintained at elevated current densities on Cd–Fe₂O₃.</p><p></p>