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To better understand the thermal decomposition and reaction process of a fluorine-containing powdery thermite, PTFE/Al/MnO₂, reactions at different temperatures were investigated by the TG/DSC-MS technique. The corresponding reaction products were characterized with XRD phase analysis. Another three thermite materials, i.e., PTFE/Al, Al/MnO₂, and PTFE/MnO₂, were also prepared for comparison. Results showed that PTFE behaved as both oxidizer and reducer in PTFE/Al/MnO₂ fluorinated thermite. The thermal decomposition and reaction process of as-fabricated ternary thermite could be divided into two stages—the mutual reaction between each of PTFE, Al, and MnO₂ and the subsequent reaction produced between Al and Mn₂O₃/Mn₃O₄/MnF₂. Compared with the three control systems, the specially designed ternary system possessed a shorter reaction time, a faster energy release rate, and a better heat release performance.