Systematic divergences in the orthopositronium (o-Ps) annihilation lifetimes, tau(3), and intensities, I-3, are observed, when comparing melt-crystallized and cold-crystallized poly(ethylene terephthalate) (PET) as a function of crystallinity. Following a previous analysis of corresponding deviations in oxygen permeability, the divergences in I-3 and tau(3) are traced to distinct characteristic values for the probability of o-Ps formation and o-Ps lifetime in the rigid amorphous phase (RAF) associated with the crystalline lamellae and the mobile amorphous regions (MAF) which are unperturbed by the presence of the crystal phase. Utilizing independent information on the volume fractions of RAF and MAF, a quantitative analysis of the o-Ps annihilation parameters is possible.