Joint reliability of immersion Ag with two different solders, Sn–37Pb and Sn–3.5Ag, were evaluated. We first compared the interfacial reactions of the two solder joints and also successfully revealed a connection between the interfacial reaction behavior and mechanical reliability. The Sn–Pb solder produced a Pb-rich phase along the interface between the solder and the Cu substrate during aging. In contrast, the Sn–Ag solder exhibits an off-eutectic reaction to produce the eutectic phase and Ag3Sn precipitate. The shear test results show that the Sn–Pb solder joint fractured along the interface showing brittle failure indications possibly due to the brittle Pb-rich layer. In contrast, the failure of Sn–Ag solder joint was only through the bulk solder, providing evidence that the interface is mechanically reliable. The results from this study confirm that the immersion Ag/Sn–Ag solder joint is mechanically robust, and thus the combination is a viable option for a Pb-free package system.