This study presents a sustainable electrochemical method for the one-pot synthesis of cyclohexanone oxime under ambient conditions using aqueous nitrate as the nitrogen source. A Zn–Cu alloy catalyst, specifically Zn₉₃Cu₇, was developed to drive the electrochemical reduction of nitrate, which generates hydroxylamine as an intermediate. This hydroxylamine then reacts with cyclohexanone in the electrolyte to produce cyclohexanone oxime. The Zn₉₃Cu₇ catalyst achieved a 97% yield and 27% Faradaic efficiency for cyclohexanone oxime at 100 mA/cm². The study demonstrates that the adsorption of nitrogen species on the catalyst surface plays a central role in catalytic performance and product selectivity. Through experimental and computational studies, including in situ Raman spectroscopy and theoretical calculations, the researchers identified the key role of surface-adsorbed nitrogen intermediates in the reaction pathway. The work highlights the importance of controlling surface adsorption for product selectivity in electrosynthesis and provides a novel strategy for the sustainable synthesis of cyclohexanone oxime through electrochemical nitrate reduction. The study also emphasizes the potential of electrochemical nitrate reduction for producing value-added organonitrogen compounds.This study presents a sustainable electrochemical method for the one-pot synthesis of cyclohexanone oxime under ambient conditions using aqueous nitrate as the nitrogen source. A Zn–Cu alloy catalyst, specifically Zn₉₃Cu₇, was developed to drive the electrochemical reduction of nitrate, which generates hydroxylamine as an intermediate. This hydroxylamine then reacts with cyclohexanone in the electrolyte to produce cyclohexanone oxime. The Zn₉₃Cu₇ catalyst achieved a 97% yield and 27% Faradaic efficiency for cyclohexanone oxime at 100 mA/cm². The study demonstrates that the adsorption of nitrogen species on the catalyst surface plays a central role in catalytic performance and product selectivity. Through experimental and computational studies, including in situ Raman spectroscopy and theoretical calculations, the researchers identified the key role of surface-adsorbed nitrogen intermediates in the reaction pathway. The work highlights the importance of controlling surface adsorption for product selectivity in electrosynthesis and provides a novel strategy for the sustainable synthesis of cyclohexanone oxime through electrochemical nitrate reduction. The study also emphasizes the potential of electrochemical nitrate reduction for producing value-added organonitrogen compounds.