The organic electrical insulator polytetrafluoroethylene (PTFE) is used in aerospace industry under extreme conditions of temperature and electric field. The melting temperature of PTFE is about 327°C and nowadays operating temperature of this kind of insulators can reach about 300°C and up to 350°C for new generations of machines. All thermal, electrical and mechanical operating stresses, especially high temperature and voltage can be factors of ageing acceleration and/or degradation of the insulators that could cause premature failures. Our present work is focused on the organic insulator behavior at high temperature in order to understand the mechanisms of thermal ageing and degradation. The change of morphology of PTFE during the thermal ageing has been studied. Thin films in PTFE were aged by accelerated method under oxidizing environment (air) and severe thermal constraints between 340 and 450°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39841.