SnBi eutectic thin film alloys are widely used in microelectronic devices, sensors, biomedical devices due to their high resistance, low temperature coefficient, chemical stability, and biocompatibility. However, the large standard electrode potential difference (454 mV) between Sn (−0.136 V) and Bi (+0.3118 V) makes them difficult to be co-deposited, especially with eutectic composition. In this study, cathodic polarization curves were used to analyze the negative shift of the cathodic reduction potentials of Sn and Bi induced by gelatin and EDTA-2Na, respectively, which reduced the potential difference between the two to 184 mv (Sn:-0.958 v; Bi:-0.774 v) and enabled the co-deposition of Sn and Bi; cathodic overpotentials were analysed to show that catechol not only improves the degree of cathodic polarization, but also raises the overpotentials, resulting in flatter surface coatings; By adjusting the temperature, current density, and pulse current, a SnBi eutectic thin film coating with good weldability, controllable thickness, flat surface, density, and uniformity was obtained on copper foil using a platinum as the anode in a methanesulfonic acid solution. The results indicate that it is feasible to deposit SnBi solder alloy at eutectic points (Sn41.53Bi58.47, At.%). Under the synergistic effect of gelatin and unidirectional square wave pulse, a typical eutectic network morphology can be obtained, which is the same as the microstructure of industrial SnBi eutectic solder. Based on these, a core-shell composite soldering material for low-temperature soldering was obtained by using SAC305 solder balls as cores and a SnBi low-temperature soldering material coating was roll-plated on their surfaces. This study provides a reliable technical way and theoretical guidance for low-temperature soldering, preparation of low-temperature solderable core-shell composite soldering material, and application of sensors and optoelectronic devices.