A series of syndiotactic polystyrene (SPS) samples in β crystalline form were prepared by cooling from the melt at various cooling rates. The effects of cooling rate from the melt, and DSC heating rate on the multiple melting behaviors of β crystals were investigated by differential scanning calorimetry (DSC) and modulated differential scanning calorimetry (MDSC), from which the nature of the multiple melting behavior was ascribed to the occurring of a recrystallization process.