The sintering behavior of Ni electrode alloyed with Cu and the interfacial structure between Ni/Cu to BaTiO3 (BT) have been investigated. The quantitative properties, which include thermal shrinkage, thermal expansion, wetting behaviors of Ni/Cu alloys on BT sheet, and composition distribution were measured by several thermal analysis techniques (TGA/DTA/TMA) and microstructural techniques (SEM/TEM/ HRTEM) with energy-dispersive spectroscopy (EDS). The shrinkage of the Ni/Cu/ BaTiO3 composite tested in 5%H2/N2 atmosphere showed strong influence by the addition of Cu, and retarded slightly due to the addition of the BT particulates. The Cu alloyed with Ni improves the continuity of the electrode and does not trigger mutual reaction between Ni and BT.