Syndiotactic poly(propylene)s (s-PPs) were freeze-dried from toluene solutions of various concentrations. FT-IR spectroscopy and wide-angle X-ray diffraction were used to characterize the s-PPs prepared. The isothermal crystallization behavior was also investigated by means of differential scanning calorimetry. The disentangled particles are of high crystallinity and show crystallization rates. A trans-planar conformation is developed when s-PP was freeze-dried from more dilute solution.