Reactive metals (RMs) are a new class of material that can withstand mechanical loads and chemically react to release large amounts of heat under strong impact loading. They are gradually becoming widely used in defense and military fields, including for high-efficiency warheads and reactive armor. For the numerical simulation method considering the combined mechanical-thermo-chemical process for the impact energy release behavior of the RMs, the Al/Ni-based RMs were investigated in this work by combining experiments, theoretical calculations and a numerical simulation. Three kinds of Al/Ni-based RMs (Al-Ni, Al-Ni-CuO and Al-Ni-MoO₃), were prepared using the hot-pressing forming process. Firstly, the compressive behavior and the parameters of the Johnson-Cook constitutive model were obtained using a mechanical testing machine and split Hopkinson pressure bars (SHPB). Secondly, the parameters of the equation of state (EOS) under the medium and low pressure conditions of the Al/Ni-based RMs, which were was seen as porous mixtures with high theoretical material density percentages (TMD%), were calculated based on the cold-energy superposition theory and the Wu-Jing method. Third, the impact energy release behaviors of the three RMs were studied with direct ballistic tests. The shock temperatures at different impact velocities were calculated based on the existing shock-induced chemical reaction thermo-chemical model while considering the chemical reaction efficiency, the relationship between the shock temperature and the extent of the chemical reaction was established, and the parameters of the relevant chemical kinetic equations were fitted. Finally, the user’s subroutines defining the material model were implemented to update the stresses in the solids elements in LS-DYNA. The model was based on the Johnson-Cook constitutive model with consideration of the mechanical-thermo-chemical coupling effect, which was verified by the experimental results. The results show that the constitutive model developed in this work can describe the impact energy release behavior of the Al/Ni-based RMs.