Based on the Ti-B4C-sucrose(precursor of carbon) -5wt.% Al sprayed system, the self-reactive spray formed multi-phased structural ceramic preforms tests were done. And the organization, structure and performances of the products were studied. The results show that the products are composed of continuous matrix phase TiC0.3N0.7, dispersed micro/nanometric rodlike grains TiB2, some of Al2O3, pores and intermetallic phase Ti3Al which is hard to identify by SEM. Aluminum is benefit to improve organization, structure and performances of the products. The average density of the products is 97.7%, the Vickers hardness is 20.6GPa, and the flexural strength is 425MPa. There are crack deflection and grain bridging toughening mechanisms owing to the rodlike grains of TiB2 in the products, which makes their fracture toughness is as high as 7.3MPa•m1/2.