The novel ceramic/metal composite materials were successfully fabricated by combustion synthesis in high gravity field. In this paper, the Ti–B₄C was selected as the main combustion reaction system to obtain TiB₂–TiC ceramic substrate, and the 1Cr18Ni9Ti stainless steel was selected as the metal substrate. It was found that the TiB₂–TiC/1Cr18Ni9Ti composite materials exhibited continuously graded composition and hybrid microstructure. The TiC_1-x carbides and TiB₂ platelets decreased gradually in size and volume fraction from the ceramic to stainless steel. Due to the rapid action of thermal explosion as well as the dissolution of the molten stainless steel into TiB₂–TiC liquid, the diffusion-controlled concentration gradient from the ceramic liquid to the alloy liquid was observed. Finally, as a result of the rapid sequent solidification of the ceramic liquid and the melt alloy surface, the laminated composite materials were achieved in multilevel, scale-span hybrid microstructure.