In this work, we report a near ~100% selectivity for urea from the electrochemical reduction of NO3 -and CO2 on Ag catalysts. The article is organized as follows: A detailed experimental catalyst screening is performed on the prominent catalysts. Electrochemical urea synthesis is performed on Ag catalyst by varying the applied potential, and a mechanism is proposed. The effect of the concentrations of NO3 -and CO2 on the urea FE and urea current density are studied. The stability of the Ag is assessed by performing an electrochemical urea synthesis reaction (USR) for a period of 9 h. Ag is characterized using XRD and XPS pre and post-electrolysis followed by operando FTIR studies. DFT calculations are done to understand the reaction pathways for urea formation on Ag catalysts.