The crystallization behavior of miscible syndiotactic polystyrene (sPS) and atactic polystyrene (aPS) blends with different sPS/aPS weight ratios was investigated in supercritical CO2 by using Fourier-transform infrared spectroscopy, differential scanning calorimetry, and wide-angle X-ray diffraction. Supercritical CO2 and aPS exhibited different effects on the conformational change of sPS and competed with each other. Increasing the content of amorphous aPS in the blends made its effect on the conformational change of sPS gradually surpass that of supercritical CO2. Supercritical CO2 favored the formation of the helical conformation of sPS in lower temperature range and the all trans planar conformation in higher temperature range, instead of forming the latter one only in higher temperature range in ambient atmosphere. However, increasing aPS content in the blends pushed the range for forming the helical conformation to lower temperature and made the all trans planar conformation dominant in aPS/sPS 25/75 blend after treating in supercritical CO2 above 60 degrees C. The all trans planar zigzag conformation was more favorable than the helical conformation after mixing aPS in sPS in supercritical CO2. (c) 2007 Wiley Periodicals, Inc.