The microstructural evolution and interfacial reactions of Au/Sn/Au/Au/Ni/Kovar joint were investigated during aging at 180 and 250 °C for up to 1000 h. The Au/Sn combination formed a rapid diffusion system. Even in non-annealed joint, three phases such as AuSn, AuSn 2 and AuSn 4 were formed. After initial aging at 180 °C, the AuSn, AuSn 2, AuSn 4, Au and Sn phases, which were formed after plating, were fully transformed into ζ-phase and δ-phase, and (Ni, Au) 3Sn 2 intermetallic compound (IMC) layer was observed between the ζ-phase and Kovar. As a whole, the microstructure of the joint was stable during aging at 180 °C. On the other hand, the solid-state interfacial reaction was much faster at 250 °C than at 180 °C. During aging at 250 °C, the Ni layer on the Kovar reacted primarily with the δ-phase in the solder, resulting in the formation and growth of the (Au, Ni)Sn IMC layer at the interface. After aging for 48 h, the Fe–Co–Ni–Au–Sn phase was formed underneath the (Au, Ni)Sn IMC layer. Furthermore, cracks were observed inside the interfacial layers after complete consumption of the Ni layer. The study results clearly demonstrate the need for either a thicker Ni layer or an alternative surface finish on Ni, in order to ensure the high temperature reliability of the Au/Sn/Au/Au/Ni/Kovar joint above 250 °C.