Time-resolved simultaneous synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) technique was used to investigate the phase transitions in prequenched mesomorphic isotactic polypropylene (iPP) samples during heating and annealing processes, respectively. For the heating process, it is shown that the mesomorphic-to-monoclinic phase transition is relatively faster for
the mesomorphic iPP sample obtained with the high quenching rate than that with the low quenching rate. For the former, the stability of α-monoclinic crystals formed during heating is relatively higher. As for the annealing process, WAXD and SAXS data illustrate that the higher the annealing temperature (Ta), the earlier the mesomorphic-to-monoclinic phase transition occurs. Namely, Ta controls the phase transition rate. Both heating and annealing processes show that the increase of content of α-monoclinic crystal phase is mainly at the expense of the mesomorphic phase, with the content of amorphous phase almost invariable. The isothermal crystallization kinetics for the prequenched mesomorphic iPP sample was analyzed through the Avrami equation, revealing a two-dimensional crystal growth under the diffusion-limited mechanism.