This study underlines the ceramic BaTiO3 dielectric layer adjacent to the electrode of long-term reliability-improved Ni–Sn alloy internal electrode BaTiO3-based multilayer ceramic capacitor to clarify the cause of electric barrier formation. Electron energy loss spectroscopy measurements of the Ti L3,2 near the edges and the O K near the edge structure changes to characterize the existence of an oxygen vacancy region, approximately 60 nm in width, and generated in BaTiO3 adjacent to the interface. Accordingly, the n-type semiconductor layer of BaTiO3 that originated from the oxygen vacancies, led to the formation of a rigid Schottky barrier at the interface.