Combined kinetic analysis has been applied for the first time to the thermal degradation of polymeric materials. The combined kinetic analysis allows the determination of the kinetic parameter from the simultaneous analysis of a set of experimental curves recorded under any thermal schedule. Besides, the method does not make any assumption about the kinetic model or activation energy and allows the analysis even when the process does not follow one of the ideal kinetic models already proposed in literature. In the present paper the kinetics of the thermal degradation of both polytetrafluoroethylene (PTFE) and polyethylene (PE) have been performed. It has been concluded, without previous assumptions on the kinetic model, that the thermal degradation of PTFE obeys a first order kinetic law, while the thermal degradation of PE follows a diffusion-controlled kinetic model.