Sn-Ag-Cu-Ni-Ge solder alloy has been developed to improve the mechanical properties of the Sn-Ag-Cu base solders and prevent oxidation of those solders. In this paper, an interfacial reaction and microstructure between the solder and a Cu electrode were investigated under heat exposure conditions. It was found that intermetallic compounds growth at the interface of the solder and the Cu electrode was greatly affected by amounts of added elements. Adding Ni in the solder can suppress the formation and growth of intermetallic compounds (IMCs) such as Cu-Sn and decreasing the amount of adding Ag in the solder can prevent the formation and growth of Ag3Sn. Moreover, it was found that there was an effect of suppress the growth of the Cu3Sn formed on the interface of Cu and (Cu,Ni)6Sn5 by adding Ni from analysis results of EDX and TEM.