PEN is thought to have increased thermal and hydrolytic resistance in comparison to PET. However, due to a lack of research, few studies have been published on the degradation of PEN. In our research, we report on the extent of degradation in PET and PEN after ageing under contrasting environments (dry nitrogen, dry air, wet nitrogen, and wet air) at temperatures between 140 degrees C and 190 degrees C. A combination of analysis techniques were employed in order to characterize and track the physical and chemical changes in the aged polyester samples, enabling the effects of temperature, water, and oxygen to be mapped onto the resultant property changes of PET and PEN. The extent of degradation has been shown to differ between both polymers and the dominant degradation mechanism in PET was shown to differ with ageing temperature. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011