Sn-Ag-Cu alloys are considered one of the most favorable lead-free solder systems. In slowly-cooled eutectic Sn-Ag-Cu alloys, sometimes large primary Ag3Sn or Cu6Sn5 intermetallic compounds (IMCs) form. These IMCs may affect the mechanical properties of solders. However, explanations for the formation of these IMCs are still not clear. This study deals with interrupted tests in order to clarify the nucleation of IMCs in the liquid phase. In this study, Sn-4.41Ag-0.63Cu and Sn-3.30Ag-1.47Cu alloys were prepared. According to the thermodynamic calculation, Pandat, the equilibrium solidification paths are described as follows: Sn-4.41Ag-0.63Cu :L → primary Ag3Sn → binary eutectic (Ag3Sn +Sn) → ternary eutectic; Sn-3.30Ag-1.47Cu :L → primary Cu6Sn5 → binary eutectic (Cu6Sn5 + Sn)→ ternary eutectic. The actual solidification process was different from the estimation from the equilibrium phase diagram. In the case of Sn-4.41Ag-0.63Cu, only Ag3Sn grew as a primary phase in the liquid, while in the case of Sn-3.30Ag-1.47Cu, not only primary Cu6Sn5 but also pseudo-primary Ag3Sn grew in the liquid. Ag3Sn may nucleate easily in the liquid phase, but Cu6Sn5 would not nucleate in the liquid.