A series of syndiotactic polypropylene (s-PP) fractions with constant syndiotacticities and different molecular weights have been studied through differential scanning calorimetry (d.s.c.), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering experiments. The molecular weights, molecular weight distributions, syndiotacticities and sequence distributions of this series of fractions have been characterized by gel permeation chromatography, solution nuclear magnetic resonance and Fourier transform infra-red spectroscopy. The equilibrium melting temperature of sufficiently high molecular weight (above 40 000) s-PP with about 94% racemic dyads is 160 +/- 1-degrees-C, and the heat of fusion is 8.0 +/- 0.3 kJ mol-1. Overall crystallization rates exhibit a molecular weight dependence and a discontinuity with respect to crystallization temperature for the fractions. The temperature at which this discontinuity happens is at an undercooling of ca. 50-degrees-C. Based on nucleation theory, this discontinuity may be recognized as a regime III to regime II transition. With decreasing undercooling (increasing crystallization temperature) and molecular weight, a doubled crystal unit cell along the b axis becomes increasingly dominant during the crystallization. In this unit cell, opposite handedness of the helical chains exists along both the a and b axes (antichiral packing). Double melting peaks can be observed for all fractions in the high to middle undercooling region (DELTAT > 50-degrees-C), while only one melting peak can be found in the relatively low undercooling region. Different heating rate experiments after isothermal crystallization in d.s.c. and WAXD indicate that the low-melting crystal may undergo reorganization and melt-recrystallization processes to form the high-melting crystal. During this transformation, doubling of the crystal unit cell along the b axis with an antichiral packing of the chain molecules is obtained.