Differential scanning calorimetry (DSC) is used in the present study to determine the onset temperature of phase transformation and the enthalpy of fusion of various solder alloys. The solders studied are Sn-Pb, Sn-Bi, Ag-Sn, In-Ag, and Sn-Pb-Bi alloys. Very notable undercooling, such as 35 ЊC, is observed in the solidification process; however, a superheating effect is not as significant in the heating process. Besides the direct measurements of reaction temperature and heat of fusion, the fraction solid vs temperature has also been determined using a DSC coupled with a mathematicalmodel method. The heating and cooling curves of the solders are first determined using DSC. By mathematically modeling the heat transfer of the DSC cells, the heat evolution and absorption can be calculated, and then the melting and solidification curves of the solder alloys are determined. The three ternary alloys, Sn-35 wt pct Pb-10 wt pct Bi, Sn-45 wt pct Pb-10 wt pct Bi, and Sn-55 wt pct Pb-10 wt pct Bi, displayed similar DSC cooling curves, which had three reaction peaks. However, the solid fractions of the three alloys at the same temperature in the semisolid state, which had been determined quantitatively using the DSC coupled with a mathematical method, were different, and their primary solidification phases were also different.