The goal of this research is to study the applicability of the diffusion boriding process as a high-temperature thermochemical heat treatment to enhance the lifetime of steel selective soldering tools. The main purpose of the work is to discuss the behavior of double-phase (FeB/Fe2B) iron-boride coating on the surface of different steels (DC04, C45, CK60, and C105U) against the stationary SAC309 lead-free solder liquid alloy. The boride coating was formed on the surface of the steel samples through the powder pack boriding technique. The microstructure of the formed layer was examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The borided samples were first cut in half and then immersed into a stationary SAC309 lead-free solder liquid alloy (Sn–3Ag–0.9Cu) for 40 days. Microstructure examinations were performed by SEM with energy-dispersive spectroscopy and an elemental distribution map after the dissolution test. Excessive dissolution/corrosion of the original steel surface was observed at the steel/SAC interfaces, leading also to the formation of Fe–Sn intermetallic phases. This was found to be the major reason for the failure of selective soldering tools made of steel. On the contrary, no dissolution and no intermetallic compounds were observed at the FeB/SAC and at the Fe2B/SAC interfaces; as a result, the thicknesses of the FeB and Fe2B phases remained the same during the 40-day dissolution tests. Thus, it was concluded that both FeB and Fe2B phases show excellent resistance against the aggressive liquid solder alloy. The results of the dissolution tests show a good agreement with the thermodynamic calculations.