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The initial stage of thermal and radiation-enhanced thermal depolymerization over the temperature range of 310–460°C in vacuum was studied for polytetrafluoroethylene specimens with different thicknesses. Conditions for the occurrence of depolymerization in the kinetic and diffusion regions were determined. The specific features of depolymerization kinetics for low-molecular-mass polytetrafluoroethylene specimens obtained by preliminary irradiation of virgin samples at room temperature were revealed. A possible role of depolymerization in radiation crosslinking of polytetrafluoroethylene irradiated above the crystallite melting point was considered.