Industrial urea synthesis is performed under harsh conditions requiring huge energy consumption and accompanied by heavy environmental pollution. Electrocatalytic C− N coupling for valuable urea synthesis from the coreduction of CO 2 and an inexpensive nitrogen source, such as N 2 , nitrite, nitrate, and NO, under ambient conditions is a potential green and sustainable substitute for the harsh industrial process. However, the nuts and bolts of electrocatalytic urea synthesis are seldom systemically reviewed. In this Perspective, theoretical and experimental research progress toward urea electrosynthesis is introduced and critically highlighted. From the view of the reaction pathway for the generation of urea molecules, chemiadsorption and activation of inert molecules (CO 2 or N 2 ) and the subsequent C−N couplings are the most important steps to determine the efficiency and selectivity of electrocatalytic reactions. The mechanisms of C−N coupling and hydrogenation toward urea formation in the above progress are summarized and rigorously estimated. This perspective reviews the exploration and preparation of electrocatalysts for urea synthesis with high efficiency and selectivity.