The influence of crystallization temperature on formation of the α- and β-form crystals of syndiotactic polystyrene (sPS) was investigated by X-ray diffraction and non-isothermal differential scanning calorimetry analysis. For sPS samples without any thermal history, the crystallization temperature must be the intrinsic factor controlling the formation the α and β-form crystals. Being crystallized at different cooling rate from the melt, sPS forms the β-form crystal until the temperature cooled down to about 230°C, and α-form crystal can only be obtained when the temperature was below about 230°C.