Secondary thermal shrinkage or chemical shrinkage involved in the thermal shrinkage of polyacrylonitrile (PAN) fibers was not only associated with the cyclization degree but also the thermal mobility of molecular chains in the aggregation structures during crosslinking. In this study, the cyclization process was monitored with differential scanning calorimetry and IR spectroscopy. The evolution of aggregation structures throughout cyclization and variations in the secondary shrinkage for the PAN fibers were characterized with wide-angle X-ray diffraction and thermal mechanical analysis, respectively. The results show that with increasing temperature, the cyclization degree increased; the cyclization occurred first in amorphous regions and then extended to the crystalline regions. Correspondingly, the secondary shrinkage also increased and could be separated into two stages: those of the amorphous and crystalline phases. The shrinkage of the crystalline regions was much bigger than that of the amorphous regions. For fibers with different aggregation structures, the crystallinity affected the cyclization degree in the amorphous and crystalline regions and resulted in the difference in total shrinkage. Furthermore, because the unoriented molecular chains in both the amorphous and crystalline regions shrank more after cyclization, the shrinkage of both regions was primarily decided by the level of orientated molecular chains participating in the cyclization. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012