The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS 13 C NMR. Proton T 2 , 13 C T 1r , and proton T 1r decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T 2 and 13 C T 1r measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T 1r , on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of 13 C T 1r values on two different irradiating field strengths (H 1 Å 38 KHz, H 1 Å 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O 2 and CO 2 gas permeabilities in PET, PEI, and PEN.