The paper describes the structural and phase composition of TiHf50, AlHf50, TiAl49Hf2 composite materials obtained by the “hydride” technology. A three-component phase diagram for Ti-Al-Hf at 1150°C is constructed. The structural state of TiAl49Hf2 alloys was predicted based on reference lattices found in the USPEX code with the VASP interface; quantum-chemical calculations of the TiAl49Hf2 energy were additionally performed in the CASTEP code. It is shown that solid solutions dominate in the TiAl49Hf2 alloy sample, in which the main elements dominate: Al10 – Ti9Al23 – Ti8. Hf atoms can be introduced into the interstitial sites [-0.257 0.042 0.2545] (St-Hf-27), [0.0053 -0.0120 -0.0765] (St-Hf-143), [0.5 0.5 0.5] (St-Hf). The introduction of hafnium into the specified lattice sites does not violate the stabilizing effect in the TiAl49Hf2 systems. It is shown that the maximum microhardness value (4.9 GPa) was obtained when testing the TiHf50 sample (for comparison: for the TiAl50 system – 1.2 GPa, for the TiAl49Hf2 system – 2.2 GPa).