The supermolecular structures of poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), and their blend were investigated with optical microscopy and small angle light scattering. With increasing the crystallization temperature, incomplete spherulitic texture was developed for the PET samples. At a high crystallization temperature of 220 ℃, the light scattering pattern represented a random collection of uncorrelated lamellae. The general morphological appearances for the PEN samples were similar to that of the PET. A notable feature was that the spherulites of the PEN formed at 200 ℃ showed regular concentric bands arising from a regular twist in the radiating lamellae. The spherulitic morphology of the PET/PEN blend was largely influenced by the changes of the sequence distribution in polymer chains determined by the level of transesterification. The increased sequential irregularity in the polymer chains via transesterification caused a morphological transition from a regular folded crystallite to a tilted lamellar crystallite.