This study reports an electrochemical method for the one-pot synthesis of cyclohexanone oxime, an important precursor for Nylon-6, under ambient conditions using aqueous nitrate as the nitrogen source. A series of Zn–Cu alloy catalysts were developed to drive the electrochemical reduction of nitrate, where the hydroxylamine intermediate formed during the electroreduction process reacts with cyclohexanone to produce the desired oxime. The optimal performance was achieved with a Zn0.9Cu0.1 electrocatalyst, achieving a 97% yield and a 27% Faradaic efficiency for cyclohexanone oxime at 100 mA/cm². In-depth mechanistic studies, including in situ Raman spectroscopy and theoretical calculations, revealed that the adsorption of nitrogen species plays a central role in the catalytic performance. The results highlight the potential of using electrochemical nitrate reduction to upgrade waste nitrate into valuable organonitrogen compounds while controlling surface adsorption for product selectivity in electrosynthesis.This study reports an electrochemical method for the one-pot synthesis of cyclohexanone oxime, an important precursor for Nylon-6, under ambient conditions using aqueous nitrate as the nitrogen source. A series of Zn–Cu alloy catalysts were developed to drive the electrochemical reduction of nitrate, where the hydroxylamine intermediate formed during the electroreduction process reacts with cyclohexanone to produce the desired oxime. The optimal performance was achieved with a Zn0.9Cu0.1 electrocatalyst, achieving a 97% yield and a 27% Faradaic efficiency for cyclohexanone oxime at 100 mA/cm². In-depth mechanistic studies, including in situ Raman spectroscopy and theoretical calculations, revealed that the adsorption of nitrogen species plays a central role in the catalytic performance. The results highlight the potential of using electrochemical nitrate reduction to upgrade waste nitrate into valuable organonitrogen compounds while controlling surface adsorption for product selectivity in electrosynthesis.