Electrocatalytic nitrate (NO3 -) reduction to ammonia (NRA) offers a promising pathway for ammonia synthesis. The interfacial electronic interactions (IEIs) can regulate the physicochemical capabilities of catalysts in electrochemical applications, while the impact of IEIs on electrocatalytic NRA remains largely unexplored in current literature. In this study, the high-efficiency electrode Ag-modified Co3O4 (Ag1.5Co/CC) is prepared for NRA in neutral media, exhibiting an impressive nitrate conversion rate of 96.86 %, ammonia Faradaic efficiency of 96.11 %, and ammonia selectivity of ~100 %. Notably, the intrinsic activity of Ag1.5Co/CC is ~81 times that of Ag nanoparticles (Ag/CC). Multiple characterizations and theoretical computations confirm the presence of IEIs between Ag and Co3O4, which stabilize the CoO6 octahedrons within Co3O4 and significantly promote the adsorption of reactants (NO3 -) as well as intermediates (NO2 - and NO), while suppressing the Heyrovsky step, thereby improving nitrate electroreduction efficiency. Furthermore, our findings reveal a synergistic effect between different active sites that enables tandem catalysis for NRA: NO3 - reduction to NO2 - predominantly occurs at Ag sites while NO2 - tends to hydrogenate to ammonia at Co sites. This study offers valuable insights for the development of high-performance NRA electrocatalysts.