The melting behavior of syndiotactic polypropylene (s-PP) after isothermal crystallization from the melt state was studied using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) techniques. Three melting endotherms were observed for isothermal crystallization at high degrees of undercooling. The minor endotherm, located closed to the corresponding crystallization temperature, was postulated to be the melting of the secondary crystallites formed at the crystallization temperature. The low-temperature melting peak was found to be the melting of the primary crystallites formed, and the high-temperature melting peak was a result of the melting of the crystallites recrystallized during a heating scan. The triple-melting behavior observed in subsequent melting endotherms of s-PP was therefore described as contributions from melting of the secondary crystallites and their recrystallization, partial melting of the less stable fraction of the primary crystallites and their recrystallization, melting of the primary crystallites, and remelting of the recrystallized crystallites formed during the heating scan. In addition, determination of the equilibrium melting temperature for this s-PP resin according to the linear and nonlinear Hoffman-Weeks extrapolations provided values of 143.1 and 185.6 degreesC, respectively.