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• In present study, a detailed investigation on the ablation behavior of the layered structure by computational and experimental methods. • The multilayer alternating structure HS coating performed better ablation resistance compared with single layer SiC and HfC coating. • The multi-layer structure can effectively inhibit the propagation of cracks in the coating during ablation. To improve the service life of carbon/carbon (C/C) composites under ultra-high temperature ablation environments (> 2200 ℃), SiC/HfC coating with multi-layer alternating structure was designed and prepared on C/C composites by low-pressure chemical vapor deposition (LPCVD). The microstructure and phase compositions of the as-prepared and ablated coatings were investigated, and the influence of the multi-layer structure on the ablation behavior and thermal stress distribution of the coatings were analyzed as well. After ablation for 120 s, the (SiC/HfC) 3 coating has better ablation resistance due to its multi-layer structure and the formation of Hf-Si-O sticky glass phase. [ABSTRACT FROM AUTHOR]