Polyacrylonitrile (PAN) fibers of a special grade have been modified by a method of prestretching with various stretching ratios from negative to positive before the onset of stabilization. The effect of such pretreatments on the thermorhelogical and thermal behaviors of PAN fibers was followed by free shrinkage experiments and differential scanning calorimetry (DSC) analyses. It was found that prestretching had a significant influence on the physical shrinkage of PAN fibers. DSC results of PAN fibers showed dependence not only on atmospheric conditions but also on the extent of prestretching.