BackgroundLow carbonization and Restriction of Hazardous Substances (RoHS) regulations have promoted the development of low-temperature lead-free solder. The solder and substrate are critical entities of joint connections. MethodsSn58Bi has been considered a promising low-temperature solder. Electroless nickel/electroless palladium/immersion gold (ENEPIG) is a good surface finish that prevents solder joints from oxidizing and extends the shelf life of the substrates. In this study, the interfacial reactions between the Sn58Bi solder and ENEPIG surface finish were systematically analyzed. Findings(Au,Pd,Ni)(Sn,Bi)4 was observed after reflow at 160 °C. Au and Pd dissolved into solder rapidly in the beginning. NiSn4 and Ni3Sn4 with small amounts of Au and Pd dissolution formed at the interface after aging. The morphology of NiSn4 evolved from block-like to needle-shaped and finally to a layered configuration as the aging temperature and time increase. Ni3Sn4 was observed between NiSn4 and substrate above 100 °C. This study established the growth mechanism of intermetallic compounds (IMCs) in the reaction between Sn58Bi and ENEPIG for low-carbon emitting processes.