Fluoropolymers get increasing attention in energetic materials application due to the high fluorine content. To explore the effect of poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) on Al/MnO2 nanothermite, the samples with different contents are prepared and characterized by SEM, TG-DSC, XRD, and their ignition and combustion behavior are tested and recorded. The results show that P(VDF-HFP) as an energetic binder can combine the nanothermite components together, even exist in the gaps. The integrity of energetic materials has been improved. Thermal analysis shows that the addition of P(VDF-HFP) greatly changes the thermal reaction processes, and the exothermic peaks appear early, but the utilization of fuel and oxidizer is not efficient from the XRD results. Furthermore, the appropriate addition of P(VDF-HFP) can directly reduce the ignition energy threshold and increase the combustion time, which is necessary for the potential ignition charge application. The possible reasons for above phenomena are discussed and analyzed. This research provides a reference for improvement of thermite-based ignition charge formulation.