Structurally rigid copolyester thermoplastics were synthesized from 1,4-cyclohexanedimethanol and the diesters dimethyl biphenyl-4,4 '-dicarboxylate and dimethyl 2,6-naphthalenedicarboxylate (DMN) via conventional melt transesterification. Conventional differential scanning calorimetry (CDSC) showed all compositions to exhibit multiple endotherms upon heating. Wide-angle X-ray diffraction analysis showed copolyester compositions to exhibit the crystalline structure of either the homopolyester Poly(1,4-cyclohexylenedimethylene 2,6-naphthalate) (PCN) or the homopolyester Poly(1,4-cyclohexylenedimethylene 4,4 '-bibenzoate) (PCB), but not both simultaneously. Further thermal analysis using CDSC and fast DSC investigated the origin of the multiple endotherm behavior. While three endotherms are observed for low heating rates, the upper two endotherms appear to merge at heating rates about 1-5 degrees C s(-1) and a single endotherm remains above heating rates about 10-50 degrees C s(-1). While the behavior of the upper two endotherms is undeniably consistent with the mechanism of melting-recrystallization-remelting (MRR), we suggest that the low endotherm is likely associated with the melting of constrained secondary crystals, although MRR effects cannot be ruled out. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 973-980