The temperature behavior of the IR and EPR spectra of the industrial polytetrafluoroethylene F-4 sample and ultradisperse polytetrafluoroethylene (UPTFE) sample obtained by the thermogas dynamic method has been studied. It is shown that the spiral-chain conformation is preserved for both structures and that ordering tends to increase at lower temperatures. The IR spectral parameters of UPTFE were found to change irregularly at 273 K and 233 K due to a rearrangement of the crystalline component of the polymer. The observed temperature changes in the EPR spectra of the middle radicals in the samples are caused by gradual freeze-out of the molecular motions in UPTFE to a temperature ∼25° lower than in F-4, due to differences in the molecular and supramolecular structures of the samples.