Micrometer-sized aluminum is widely used in energetics; however, performance of propellants, explosives, and pyrotechnics could be significantly improved if its ignition barriers could be disrupted. We report morphological, thermal, and chemical characterization of fuel rich aluminum-polytetrafluoroethylene (70–30 wt-%) reactive particles formed by high and low energy milling. Average particle sizes range from 15–78 μm; however, specific surface areas range from approx. 2–7 m2 g−1 due to milling induced voids and cleaved surfaces. Scanning electron microscopy and energy dispersive spectroscopy reveal uniform distribution of PTFE, providing nanoscale mixing within particles. The combustion enthalpy was found to be 20.2 kJ g−1, though a slight decrease (0.8 kJ g−1) results from extended high energy milling due to α-AlF3 formation. For high energy mechanically activated particles, differential scanning calorimetry in argon shows a strong, exothermic pre-ignition reaction that onsets near 440 °C and a second, more dominant exotherm that onsets around 510 °C. Scans in O2-Ar indicate that, unlike physical mixtures, more complete reaction occurs at higher heating rates and the reaction onset is drastically reduced (approx. 440 °C). Simple flame tests reveal that these altered Al-polytetrafluoroethylene particles light readily unlike micrometer-sized aluminum. Safety testing also shows these particles have high electrostatic discharge (89.9–108 mJ), impact (>213 cm), and friction (>360 N) ignition thresholds. These particles may be useful for reactive liners, thermobaric explosives, and pyrolants. In particular, the altered reactivity, large particle size and relatively low specific surface area of these fuel rich particles make them an interesting replacement for aluminum in solid propellants.