Three poly(ethylene terephthalate) films were prepared having the same crystallinity but different morphology. They were colored with azo dyes XC6H4N = NC6H4N(C2H5)2 (where X is H, OCH3, CN, and COOC2H5). The kinetics of the thermal cis-trans isomerization of these dyes has been studied below the glass transition temperature in the range 25–56°C. The isomerization process was found to be the result of a multiplicity of first-order reactions. The kinetic parameters have been correlated with the order degree at molecular level of the polymer. Lightfastness of the dyes in the polymer matrices has been also investigated: it appeared to be in relation with the supermolecular structure of the film.