The electrocatalytic NO3- reduction reaction (NO3RR) to NH3 provides a promising pathway for ambient NH3 synthesis and environmental pollution treatment. Cu and its oxides are recognized as effective NO3RR electrocatalysts due to their favorable d-orbital energy levels and superior kinetics. In this work, mixed-valence Cu-based catalysts with tunable valence states were constructed via an inorganic salt-induced MOF-derived strategy. Notably, optimized Cu-CuxO/C-0.3 featured a Cu/Cu2O heterostructure and demonstrated the lowest Cu valence state. The resulting Cu/Cu2O heterointerface facilitated electron transfer and increased the density of electrochemically active sites, leading to an enhanced faradaic efficiency of 81.4% and a remarkable yield rate of 13.38 mg h-1 cm-2 (ca. 2.39 mol h-1 gcat.-1) at -0.8 V vs. RHE. This work presents insights for designing multi-phase heterostructured NO3RR catalysts and emphasizes their potential significance in efficient ammonia production.