The Al-Ni-Ti-Zr non-equilibrium alloy powder was prepared by mechanical alloying method. The Al-Ni-Ti-Zr non-equilibrium alloy powder/polytetrafluoroethylene(PTFE) reactive materials were prepared via mixing/pressing using Al-based non-equilibrium alloy powders and PTFE micro powders. The phase composition and morphology characteristics of the powders during ball milling were characterized by X ray diffraction(XRD) and scanning electron microscopy(SEM). The phase structure of the milled alloy powders was analyzed by high resolution transmission electron microscopy(HRTEM) and selected area electron diffraction(SAED). The thermal behaviors of non-equilibrium Al/PTFE reactive materials were examined by differential scanning calorimetry(DSC). The results show that the Al-based non-equilibrium alloy powders can be prepared by mechanical alloying method. There is a nano scale micro-crystalline island area dispersed in amorphous phase matrix. The peak temperature and exothermic peak area of non-equilibrium Al/PTFE reactive materials at a heating rate of 10 K·min^-1 in air are 495 ℃ and 1775 J·g^-1, respectively. Under the continuous heating condition, the exothermic reaction of the non-equilibrium Al/PTFE reactive materials has the typical kinetic characteristics, and the activation energy E_c of the reaction is calculated as 309.1 kJ·mol^-1 by Kissinger method.