AbstractBased on the cross‐linking reaction of bisphenol A epoxy resin and liquid carboxy‐terminated poly(tetrafluoroethylene‐hexafluoropropylene‐vinylidene fluoride) copolymer (CTTHV), the elastomer containing fluoroolefin segment was prepared. The bis(2,2‐dinitropropyl)‐acetal/formal (BDNPA/F) was used as an energetic plasticizer for this fluoroolefin segment‐containing elastomer (FO elastomer). The compatibility of CTTHV and BDNPA/F was evaluated by the combination of differential scanning calorimetry (DSC) and derivative thermogravimetry (DTG) methods. Thermal decomposition of the FO elastomers was investigated by TG‐DSC. The kinetic parameters of the FO elastomers were calculated by Kissinger‐Akahira‐Sunose method. DSC‐TG‐MS‐Fourier transform infrared spectroscopy analysis was used to detect the thermal decomposition products. The thermal decomposition mechanisms of the FO and FO/BDNPA/F elastomers were discussed. The results show that CTTHV has a good compatibility with BDNPA/F, and the prepared FO/BDNPA/F elastomers have good thermal stability. BDNPA/F can promote the thermal decomposition of the FO elastomer and bring more heat for the binder system according to the thermal decomposition behaviors and kinetic calculation results of FO/BDNPA/F elastomers. The FO elastomer preferentially undergoes depolymerization, HF elimination with the formation of polyene sequences, and subsequent main‐chain cleavage, polyaromatization. The H ion fragments of the decomposition of BDNPA/F can be an important factor in the improvement of HF concentration at the initial thermal decomposition of FO elastomer. An abundant HF released during all decomposition of FO/BDNPA/F elastomers may be beneficial to the ignition and combustion of aluminum particles in future applications.