Self-propagating high-temperature synthesis was used to prepare boride-based functionally graded materials (FGMs) as thermal barriers for space re-entry vehicles. FGMs are characterized by inhomogeneous spatial composition, resulting in different spatial characteristics. In this work, the FGMs were composed of a ceramic [i.e., MB2 (M = Ti, Zr, Hf)] and a metallic (i.e., NiAl) side, joined together by composite layers of graded stoichiometries of the two components. Thus, in the same material, the boride end gives thermal insulation, while the intermetallic end offers an easy junction to the structure of the space aircraft. The prepared FGMs showed good adhesion between the layers and global compactness after preparation and thermal tests. The microhardness along the samples was measured, and their insulating capabilities were evaluated.