Abstract Thermal degradation of Teflon was investigated by thermoanalytical methods (TG and DTA). In the kinetic analysis of the experimental data, the NPK method proves to be a valuable tool, allowing for some new kinetic aspects of the degradation process to be obtained. Analysis of the computed isothermal and isoconversional vectors provided some insight into the reaction kinetics. Two different initiation pathways were suggested to control the global degradation kinetics, their relative contribution being temperature-dependant