Abstract Electrocatalytic C–N coupling technology offers a promising route for green and sustainable urea synthesis. However, this route faces challenges of low urea yield and Faradaic efficiency due to the high dissociation energy of atomic bonds in reactants, complex reaction intermediates, high reaction energy barriers, and competing side reactions. As C–N coupling involves the synergistic action of two or more active sites, it is crucial to develop efficient multi-active-site catalysts to address these challenges. This review analyzes the reaction mechanisms of electrocatalytic C–N coupling for urea synthesis and summarizes effective strategies to achieve multi-active-site catalysts, including heteroatom doping, defect engineering, heterojunctions, and diatomic catalysts. Furthermore, based on this analysis, we propose the universal design principles for high-efficiency multi-activesite catalysts.