In this paper, presents surface modification of Cu substrates by electroplating or chemical plating to obtain high-quality Ni and Ni–P coatings. The Sn58Bi solder reactions with Cu, Ni, and Ni–P UBMs at 180 °C, 250 °C, and 320 °C, respectively. Research has found that Ni and Ni–P substrates can inhibit Bi phase segregation and interfacial IMC overgrowth in Sn–Bi solder joints. Bi phase segregation occurs during the transition from Cu6Sn5 to Cu3Sn. There is Bi segregation at the interface of Sn58Bi/Cu solder joints to Cu3Sn/Cu interface, and IMC grows rapidly. However, Ni/Cu and Ni–P/Cu substrates can not only suppress the Bi phase segregation behavior of Sn58Bi solder joints during soldering, but also slow down the excessive growth of interfacial IMC; Even under the harsh soldering process of up to 320 °C for 600 s, it still has an effective blocking effect. In addition, at 320 °C, when Sn58Bi solder react with Cu, the interface directly crosses Cu6Sn5 to generate Cu3Sn, which exhibits the morphology characteristics of Cu6Sn5 due to high thermal conditions. During the soldering, Ni atoms continuously diffuse towards the interface, and Ni3Sn4 (Ni/Cu) grows from needle like in the early stage of soldering to rod like, and finally to block like; The block like appearance of Ni3Sn4 (Ni–P/Cu) occurs earlier than that of Ni3Sn4 (Ni/Cu), because the presence of columnar Ni3P layers provides a wider diffusion channel for Ni atoms, but the overall growth size is smaller than that on Ni/Cu. A higher undercooling can promote the growth of interfacial IMC, including Cu6Sn5 and Ni3Sn4. At the same time, the Bi phase inside the Sn58Bi solder joint is coarsened, and the substrate Ni/Ni–P can eliminate interfacial brittleness after eliminating Bi segregation.