The crystallization and multiple melting behavior of poly(phenylene sulfide) (PPS) and its blends with amorphous thermoplastic bisphenol A polysulfone (PSF) and phenolphthalein poly(ether ketone) (PEK-C), crystalline thermoplastic poly(ether ether ketone) (PEEK), and thermosetting bismaleimide (BMI) resin were investigated by a differential scanning calorimeter (DSC). The addition of PSF and PEK-C was found to have no influence on the crystallization temperature (T-c) and heat of crystallization (Delta H-c) of PPS. A significant increase in the value of T-c and the intensity of the T-c peak of PPS was observed and the crystallization of PPS can be accelerated in the presence of the PEEK component. An increase in the T-c of PPS can also be accelerated in the BMI/PPS blend, but was no more significant than that in the PEEK/PPS blend. The T-c of PPS in the PEEK/PPS blends is dependent on the maximum temperature of the heating scans and can be divided into three temperature regions. The addition of a second component has no influence on the formation of a multiple melting peak. The double melting peaks can also be observed when PPS and its blends are crystallized dynamically from the molten state.