Ni-based under-bump metallization (UBM) for flip-chip application is widely used in today's electronics packaging. In this study, electroplated Ni UBM with different thickness was used to evaluate the interfacial reaction during multiple reflow between Ni/Cu UBM and eutectic Sn–Pb solders in the 63Sn–37Pb/Ni/Cu/Ti/Si3N4/Si multilayer structure. During the first cycle of reflow, Cu atoms diffused through electroplated Ni and formed the intermetallic compound (IMC) (Ni1−x, Cux)3Sn4. After more than three times of reflow, Cu atoms further diffused through the boundaries of (Ni1−x, Cux)3Sn4 IMC and reacted with Ni and Sn to form another IMC of (Cu1-y, Niy)6Sn5. After detailed quantitative analysis by electron probe microanalysis, the values of y were evaluated to remain around 0.4; however, the values of x varied from 0.02 to 0.35. The elemental distribution of IMC in the interface of the joint assembly could be correlated to the Ni–Cu–Sn ternary equilibrium. In addition, the mechanism of (Cu1−y, Niy)6Sn5 formation was also probed.