Based on liquid fusion and interdiffusion between the ceramic and the titanium alloy, the laminated composites of TiB2-Based ceramic and Ti-6Al-4V alloy with the nano-structured gradient were achieved by centrifugal reactive casting processing. By conducting DOP test with 14.5mm army AP projectiles on TiB2-based ceramic and the laminated composite, the average ballistic mass effectiveness of two materials measured 3.05 and 7.30. Hence, it was considered that because the interlaminar interface developed the nano-structured gradient from the ceramic to Ti-6Al-4V alloy, the laminated composite not only presented high interlaminar cleavage resistance and high mechanical properties, but also exhibited high ballistic preformance by the dual mechanisms of interlaminar load transfer and multi-scale (micro/micro-nano/nanometer) interface shear-coupling.