In this paper, the physical, mechanical and friction behavior of Si3N4-Mo laminated composites were investigated. It can be found that the multilayer structure could improve the fracture toughness of laminated composite compared with pure Si3N4. Through the thermodynamic and kinetic calculations of chemical reactions, we conclude that the main product of the interface is Mo5Si3 which caused poor physical and mechanical properties of Si3N4-Mo layered ceramics. The higher content of Mo was beneficial to hinder the diffusion of cracks and improved the fracture toughness of the material, but with the lower content of Mo, Si3N4-Mo laminated ceramic composite had better tribology properity . In addition, with the increase of the load, the tribology properity of Si3N4-Mo laminated ceramic composite decreased, and the friction mechanism of Si3N4-Mo/TC4 is a mixed wear of adhesive wear and abrasive wear.