As electronic packaging technology advances towards miniaturization and integration, the issue of electromigration (EM) in lead-free solder joints has become a significant factor affecting solder joint reliability. In this study, a Sn-3.0Ag-0.5Cu (SAC305) alloy was used as the base, and different Bi content alloys, SAC305-xBi (x = 0, 0.5, 0.75, 1.0 wt.%), were prepared for tensile strength, hardness, and wetting tests. Copper wire was used to prepare EM test samples, which were subjected to EM tests at a current density of approximately 0.6 × 104 A/cm2 for varying durations. The interface microstructure of the SAC305-xBi alloys after the EM test was observed using an optical microscope. The results showed that the 0.5 wt.% Bi alloy exhibited the highest ultimate tensile strength and microhardness, improving by 33.3% and 11.8% compared to SAC305, respectively, with similar fracture strain. This alloy also displayed enhanced wettability. EM tests revealed the formation of Cu6Sn5 and Cu3Sn intermetallic compounds (IMCs) at both the cathode and anode interfaces of the solder alloy. The addition of Bi inhibited the diffusion rate of Sn in Cu6Sn5, resulting in similar total IMC thickness at the anode interface across different Bi contents under the same test conditions. However, the total IMC thickness at the cathode interface decreased and stabilized with increasing EM time, with the SAC305-0.75Bi alloy demonstrating the best resistance to EM.