A combination of dielectric relaxation, dynamic mechanical thermal analysis, and positron annihilation measurements is reported on melt-cast films of poly(ethylene terephthalate), poly(ethylene naphthalate), and their copolymers. The effects of change in the chemical structure of the polyesters are rationalized in terms of increased restriction of the mobility of the polar segments of the chain by the incorporation of the bulky naphthalate structure. All the quenched samples exhibit physical aging when raised to elevated temperatures, the rate depending on the degree of undercooling used in the aging experiments. The free volume surprisingly does not change significantly with temperature and leads to the suggestion that the reduction in the dielectric permittivity is a consequence of a reduction in the mobility of the local segments. The increased storage modulus is also consistent with a reduction in mobility. This proposal is further confirmed by the observation of a good correlation between the rates and extents of the physical aging as detected by dynamic mechanical and dielectric relaxation measurements. Similarities in the activation energies of the beta relaxation process for all the polymers investigated indicate that the dipole relaxation processes have a common origin and can be ascribed to motion of the linking polar entity. This study implies that aging is accompanied by an increase in ordering within these polyesters.