In this paper, the synthesis of four-layered functionally graded materials (FGMs) samples of (TiB2)pNi/(TiB2)p(Ni+Ni3Al)/ Ni3Al with different metallic substrate (Ni, Cu and Cr-Ni steel) by field-activated and pressure-assisted synthesis process (FAPAS) was investigated. It was shown that the imposition of the electric field and the combustion reaction of Ni3Al is the key for the successful synthesis of the FGMs during process. The exothermal reaction of the powder of nickel and aluminum during combustion enhanced the diffusion bonding in the interfaces subsequently. The microstructure, phase composition of the interfaces and mechanical properties of the graded materials were characterized, which showed indicative formation of firm bonds by the combustion reactive process. The samples have an excellent thermal shock resistance ability and gradient distribution of micro-hardness across the substrate layers and the surface layer.