Unveiling the active phase of catalytic materials under reaction conditions is important for the construction of efficient electrocatalysts for selective nitrate reduction to ammonia. The origin of the prominent activity enhancement for CuO (Faradaic efficiency: 95.8 %, Selectivity: 81.2 %) toward selective nitrate electroreduction to ammonia was probed. 15N isotope labeling experiments showed that ammonia originated from nitrate reduction. 1H NMR spectroscopy and colorimetric methods were performed to quantify ammonia. In situ Raman and ex situ experiments revealed that CuO was electrochemically converted into Cu/Cu2O, which serves as an active phase. The combined results of online differential electrochemical mass spectrometry (DEMS) and DFT calculations demonstrated that the electron transfer from Cu2O to Cu at the interface could facilitate the formation of *NOH intermediate and suppress the hydrogen evolution reaction, leading to high selectivity and Faradaic efficiency. Ammonia boost: CuO NWAs are efficient nitrate electroreduction catalysts for the selective synthesis of ammonia. In situ experiments revealed that CuO was electrochemically converted into Cu/Cu2O, which serves as an active phase. The electron transfer at the interface of Cu/Cu2O could facilitate the formation of *NOH intermediate and suppress the competitive H2 production.