<p>Electrochemical C–N bond formation is a sustainable route for producing nitrogen-containing chemicals, such as urea. However, efficient production of urea is limited by asymmetric reactant activation, insufficient interfacial co-localization and mismatched intermediate kinetics. Here an ordered symmetric–asymmetric catalytic pair (M_sym–M_asym, where M is a metal) with subnanometre spacing (~0.5 nm) is reported for urea electrosynthesis, with Cu_sym–Zn_asym facilitating a yield rate of 233.77 ± 8.89 mmol h⁻¹ g⁻¹, a Faradaic efficiency of 78.95 ± 4.17%, nitrogen selectivity of &gt;80% and carbon selectivity of &gt;97%. Mechanistic investigations indicate that coordination asymmetry between Cu_sym and Zn_asym constructs electronically complementary <i>d</i>-orbital configurations that favour the formation of weakly bound *CO on Cu_sym, enabling accumulation and migration while suppressing over-hydrogenation. Meanwhile, Zn_asym stabilizes *NO, which facilitates coupling with *CO. Subnanometre spacing between metal sites supports stepwise C–N bond formation to urea, and techno-economic analysis indicates the feasibility of low-cost and scalable production. These results verify symmetry-controlled dual-site engineering as a promising strategy for multi-intermediate electrosynthesis.</p><p></p>