Electrochemical nitrate reduction reaction (NO3RR) driven by renewable energy has attracted extensive attention which can realize nitrate degradation and ammonia production simultaneously under ambient conditions. Copper-based catalysts are the most widely used due to their high activity but are subject to low selectivity owing to intermediate nitrite accumulation. This work has reported cobalt-doped copper oxide (Co/CuO) composites, while introduced Co sites accelerate the hydrogenation of nitrogen species. The prepared Co/CuO composites realize a 93.9% Faradaic efficiency at the applied potential of -0.4 V (vs. RHE), yielding ammonia at 0.5441 mmol·h-1·cm-2. The exceptional stability of Co/CuO composites has also been affirmed by following continuous recycling tests. In situ characterization confirms that the existence of Co sites is prone to conversion of *NO2 to *NH2, thus exhibiting high performance for NO3RR.