Energetic structural materials (ESMs) are an important class of military materials due to their good structural and energy-releasing characteristics. To improve the damage effect of metal–metal ESMs with good mechanical properties, W was added to the 48Al–52Ni composites, and the effect of W on the impact-induced energy release behaviors was investigated. The results showed that the hot-press process and the addition of W did not change the microstructure and surface state of the constituent particles, leading to a stable onset temperature of the Al–Ni intermetallic reaction in (48Al–52Ni)_100-xW_x composites. Meanwhile, the decrease in the contact area between Al and Ni in the composites with increased W content resulted in the decrease in reaction heat. During the impact process, the intermetallic reaction of W caused by the Al–Ni intermetallic reaction, as well as the oxidation reaction of Al and Ni caused by the brittle fracture along the weak interface, caused the released energy of (48Al–52Ni)₄₀W₆₀ to reach 2.04 kJ/g.