Time-resolved measurements of FT-IR and Raman spectra and X-ray diffraction have been performed to trace the structural changes in the solvent-induced crystallization of syndiotactic polystyrene glass sample. After the exposure of the glassy sample into the atmosphere of such organic solvent as toluene, benzene, or chloroform, the IR and Raman bands characteristic of the regular helical conformation of (T2G2)2 type were found to increase the intensities with time. Some time delay was found for the appearance of the bands with different critical sequence lengths, leading to the concrete description of the growth of regular helical chain from the random coil. The X-ray scattering intensity began to increase largely at the timing of the appearance of the IR and Raman bands of long helical sequences, indicating that the crystal lattice starts to be formed at the timing when the long segments of regular helical form are gathered together. The rate of this crystallization process depends on the kind of the used solvent. The factors governing this difference have been discussed.