While the dimension of solder bumps keeps shrinking to meet higher performance requirements, the formation of interfacial compounds may be affected more profoundly by the other side of metallization layer due to a smaller bump height. In this study, cross interactions on the formation of intermetallic compounds (IMCs) were investigated in eutectic SnPb, SnAg3.5, SnAg3.8Cu0.7, and SnSb5 solders jointed to Cu/Cr–Cu/Ti on the chip side and Au/Ni metallization on the substrate side. It is found that the Cu atoms on the chip side diffused to the substrate side to form (Cux,Ni1−x)6Sn5 or (Niy,Cu1−y)3Sn4 for the four solders during the reflow for joining flip chip packages. For the SnPb solder, Au atoms were observed on the chip side after the reflow, yet few Ni atoms were detected on the chip side. In addition, for SnAg3.5 and SnSn5 solders, the Ni atoms on the substrate side migrated to the chip side during the reflow to change binary Cu6Sn5 into ternary (Cux,Ni1−x)6Sn5 IMCs, in which the Ni weighed approximately 21%. Furthermore, it is intriguing that no Ni atoms were detected on the chip side of the SnAg3.8Cu0.7 joint. The possible driving forces responsible for the diffusion of Au, Ni, and Cu atoms are discussed in this paper.