In conclusion, we have prepared a Zn93Cu7 alloy that can drive the one-pot electrosynthesis of cyclohexanone oxime through NO3R with a yield of 97% and FE of 27% at 100 mA/cm 2 . This electrochemical method not only enables the production of this important chemical precursor under mild conditions (room temperature, atmospheric pressure, aqueous solution, neutral pH, no toxic/expensive catalysts) compared to conventional chemical routes, but also offers a promising strategy to upgrade nitrate into value-added organonitrogen compounds. In addition, this work demonstrates the central role of the *NH2OH intermediate in this tandem EChem-Chem process, as well as the importance of controlling the surface adsorption of nitrogen species in electrosynthesis. The distinct behaviors of Zn, Cu, and ZnCu alloys observed in the experimental and theoretical studies reported in this work reveal that Cu-rich electrocatalysts can drive the NO3R at lower overpotentials to due to their strong affinity for NO3 -but favor further electroreduction of *NH2OH into NH3. In contrast, Zn-rich electrocatalysts require higher overpotentials for NO3R but facilitate the chemical reaction between *NH2OH and cyclohexanone to produce oxime. Overall, this work demonstrates a novel electrochemical strategy to upgrade nitrate and drive the sustainable synthesis of cyclohexanone oxime. This study also highlights the potential and key aspects for the development of EChem-Chem tandem processes for the electrification of industrial syntheses.