This study evaluated the time scales and chemistry of thermal decomposition and combustion of highly fluorinated polymers. Three different compounds have been studied using resistive heating to initiate thermal decomposition or combustion and FT-IR to determine the concentration time traces of several different intermediates and products. The tests indicated that the compounds produced significantly different concentrations of hydrofluoric acid, HF, when heated in a dried air atmosphere at ambient pressure. Small differences in the degree of fluorination can produce an order of magnitude change of the maximum HF concentration attained and significantly affect the time to achieve maximum HF concentration.