Physical experiments were performed to investigate the enhanced lethality of reactive materials (RMs) shaped charge liner against concrete target. The results show that the shaped charge with RMs liner left a funnel shaped hole on the pure concrete target front surfaces, whereas the Cu liner just left a slender penetration hole and produced less damage in comparison. The damage events were recorded by high‐speed photography with the frame rate up to 10,000 frames/s, and the results indicate that deflagration reaction of RMs has occurred inside the target after the detonation of main charge. By comparison of damage effects between RMs and inert Cu liners, we conclude that the gaseous products of the deflagration are the main inducement of catastrophic damage. For multi‐layered concrete targets, a cavity inside the target and several cracks on the targets front surfaces were formed, and the formation mechanisms are deeply discussed in this paper. Based on the isentropic expansion and crack growth theories, the computational formula for crack length was developed, and the influences of the mass of RMs and initiation depth on crack effects are achieved.