The methanolytic degradation of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units was investigated. Random poly(ethylene terephthalate-co-nitroterephthalate) copolyesters (PETNT) containing 15 and 30 mol % nitrated units were prepared from ethylene glycol and a mixture of dimethyl terephthalate and dimethyl nitroterephthalate. A detailed study of the influence of the nitro group on the methanolytic degradation rate of the nitrated bis(2-hydroxyethyl) nitroterephthalate (BHENT) model compound in comparison with the nonnitrated bis(2-hydroxyethyl) terephthalate (BHET) model compound was carried out. The kinetics of the methanolysis of BHENT and BHET were evaluated with high-performance liquid chromatography and H-1 NMR spectroscopy. BHENT appeared to be much more reactive than BHET. The methanolytic degradation of PET and PETNT copolyesters at 80 degreesC was followed by changes in the weight and viscosity, gel permeation chromatography, differential scanning calorimetry, scanning electron microscopy, and H-1 and C-13 NMR spectroscopy. The copolyesters degraded faster than PET, and the degradation increased with the content of nitrated units and occurred preferentially by cleavage of the ester groups placed at the meta position of the nitro group in the nitrated units. For both PET and PETNT copolyesters, an increase in crystallinity accompanied methanolysis. A surface degradation mechanism entailing solubilization of the fragmented polymer and consequent loss of mass was found to operate in the methanolysis of the copolyesters.