The diffusion and thermite reaction process of Al/NiO nanothermite composed of Al nanofilm and NiO nano honeycomb are investigated by molecular dynamics simulations in combination with the Reax FF. The diffusion and thermite reaction are characterized by measuring energy release, adiabatic reaction temperature, and activation energy. Based on time evolution of atomic configuration and mean square displacement, the initialization of the thermite reaction process of Al/NiO nanothermite results from the diffusion of Al atoms. Under the microcanonical ensemble, it is found that the adiabatic reaction temperature of the thermite reaction process of Al/NiO nanothermite reaches over 5500 K, and activation energy is 8.43 k J/mol. The release energy of the thermite reaction process of Al/NiO nanothermite is 2.2 k J/g, which is in accordance with the available experimental value. With the same initial temperature, the adiabatic reaction temperature of the thermite reaction process of Al/NiO nanothermite has a tendency to decrease dramatically as the equivalence ratio increases. On the basis of chemical bond analysis, the initial temperature and equivalence ratio have great effects on the thermite reaction process, but do not significantly affect the average length of Al–Ni nor Al–O bond. Overall, the thermite reaction of film-honeycomb Al/NiO nanothermite is a complicated process instead of a theoretical equation. The diffusion and thermite reaction process of Al / NiO nanotherm composed of Al nanofilm and NiO nano honeycomb are investigated by molecular dynamics simulations in combination with the Reax FF. The diffusion and thermite reaction are characterized by measuring energy release, adiabatic reaction temperature, and activation energy. Based on time evolution of atomic configuration and mean square displacement, the initialization of the thermite reaction process of Al / NiO nanothermite results from the diffusion of Al atoms. Under the microcanonical ensemble, it is found that the adiabatic reaction temperature of the thermite The reaction energy of Al / NiO nanothermite reaches over 5500 K, and the activation energy is 8.43 k J / mol. The release energy of the thermite reaction process of Al / NiO nanothermite is 2.2 k J / g, which is in accordance with the available experimental value. With the same initial temperature, the adiabatic reaction temperature of the thermite reaction process of Al / NiO nano thermite has a tendency to decrease dramatically as the equivalence ratio increases. On the basis of chemical bond analysis, the initial temperature and equivalence ratio have great effects on the thermite reaction process, but do not significantly affect the average length of Al-Ni nor Al -O bond. Overall, the thermite reaction of film-honeycomb Al / NiO nanothermite is a complicated process instead of a theoretical equation.