Electrochemical conversion of nitrate (NO 3 − ) into ammonia (NH 3 ) recycles nitrogen and offers a route to the production of NH 3 , which is more valuable than dinitrogen gas. However, today's development of NO 3 − electroreduction remains hindered by the lack of a mechanistic picture of how catalyst structure may be tuned to enhance catalytic activity. Here we demonstrate enhanced NO 3 − reduction reaction (NO 3 − RR) performance on Cu 50 Ni 50 alloy catalysts, including a 0.12 V upshift in the half-wave potential and a 6-fold increase in activity compared to those obtained with pure Cu at 0 V vs reversible hydrogen electrode (RHE). Ni alloying enables tuning of the Cu d-band center and modulates the adsorption energies of intermediates such as *NO 3 − , *NO 2 , and *NH 2 . Using density functional theory calculations, we identify a NO 3 − RR-to-NH 3 pathway and offer an adsorption energy−activity relationship for the CuNi alloy system. This correlation between catalyst electronic structure and NO 3 − RR activity offers a design platform for further development of NO 3 − RR catalysts.

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