Wetting properties of lead-free solders, Sn–0.7 wt.% Cu and Sn–3.5 wt.% Ag, pure Sn, and conventional Sn–40 w.t% Pb on Ni, Cu, and Ag substrates at 250 and 240 °C were determined by using a wetting balance technique. Wetting times and wetting forces were determined directly from the wetting curves, and surface tensions of molten solders were calculated from the wetting force measurements. A statistic tool, analysis of variance (ANOVA), was used to analyze the experimental results. By using the wetting time as an indication, it was found that Sn–Pb exhibited the best wetting followed by Sn–Ag, Sn–Cu, and Sn, in that order. A very significant but frequently ignored issue is that most solders react with substrates, and the molten solders are not in contact with the original substrates but rather with intermetallic compounds. On the basis of theoretical analysis and experimental observations, it was concluded that the withdrawing forces and the surface tensions of the molten solders determined by the present technique are not significantly affected by the interfacial reactions if the interfacial reactions are not too excessive. However, wetting times are strong functions of both solders and substrates and the interfacial reactions between them.