In order to obtain both high mechanical properties and released energy density, multilayered Al/Ni energetic structural materials were prepared by electrodeposition and hot pressing method in this paper. The effect of hot pressing temperature on the exothermic properties of Al/Ni energetic structural materials was studied. The damage effect of the energetic fragment on double target boards at various impact velocities was obtained through shooting experiments. The results showed that with the increase of the hot pressing temperature, the diffusion reaction at Al/Ni interfaces increased, leading to a decrease of exothermic heat from 898 J/g to 782 J/g. Under high-speed impact, the Al/Ni energetic fragment experienced a violent deflagration reaction, which had a significant damage effect on the double target boards. When the impact velocity of the energetic fragment increased from 1241 m/s to 1478 m/s, the perforation size of the main target plate was almost unchanged, however the damage area of the after-effect target plate increased significantly.