The Co/Ni–TiCN multilayer coatings with two layer, four layer and gradient structure were plasma sprayed on B 4 C ceramic matrix. The effect of the multilayer structure on the dynamic compressive properties of B 4 C matrix was investigated. The Co/Ni–TiCN coatings consisted of Co–Ni–Cr–Mo and TiC 1-X N X (0 ≤ x ≤ 1) phases. At the strain rate of 700 s −1 , the peak stress increased by ∼200% after B 4 C surface coated with multilayer Co/Ni–TiCN coatings, the energy reflectivity increased by 412% (2 layer), 850% (4 layer) and 847% (gradient), and the energy transmittance decreased by 55% (2 layer), 80% (4 layer) and 83% (gradient). At 1500 s −1 , the energy reflectivity increased by 490% (2 layer), 705% (4 layer) and 750% (gradient), and the energy transmittance decreased by 57% (2 layer), 83% (4 layer) and 89% (gradient). Compared with 2 layer structure, the 4 layer and gradient structure exhibited enhanced compressive properties because of the more layer interfaces for the reflection and transmission of the stress waves.