Based on fusion bonding and atomic interdiffusion between the liquid ceramic and molten Ti-based alloy, the laminated composites of TiB2-based ceramic and Ti-6Al-4V alloy were achieved by centrifugal reactive casting, and within the interlaminar region the composite microstructures of nano-structured gradient developed with the continously-graded evolution of TiB2 and TiB in spatial size. Interlaminar shear strength, flexural strength and fracture toughness measured 335 ± 35 MPa, 862 ± 45MPa and 45 ± 15 MPa, respectively.