PPS is increasingly interesting as a high performance polymer material. Recently, Cheng, et al. [1] reported observation of rigid amorphous phase (RAP) in the amorphous phase of semicrystalline PPS using differential scanning calorimetry. Using the heat of fusion from DSC to obtain the degree of crystallinity of the semicrystalline samples, a simple rule of mixtures was applied to calculate the change in heat capacity step. The heat capacity decreased much more than could be accounted for using the measured crystallinity. Thus, these authors assumed the existence of a rigid amorphous phase which did not become liquid-like at Tg. The ratio of heat capacity step at Tg of semicrystalline PPS to that of the purely amorphous polymer was used to find the fraction of amorphous chains that do become liquid-like at Tg. The amount of RAP was then obtained by assuming a three phase model.