This study investigates TNM-type titanium aluminide alloys, representing the third generation of β-stabilized γ-TiAl heat-resistant materials. The aim of this work is to study the combustion characteristics and to produce compact materials via the free SHS compaction method from initial powder reagents taken in the following ratio (wt%): 51.85Ti–43Al–4Nb–1Mo–0.15B, as well as to determine the effect of high-temperature isothermal annealing at 1000 °C on the structure and properties of the obtained materials. Using free SHS compression (self-propagating high-temperature synthesis), we synthesized compact materials from a 51.85Ti–43Al–4Nb–1Mo–0.15B (wt%) powder blend. Key combustion parameters were optimized to maximize the synthesis temperature, employing a chemical ignition system. The as-fabricated materials exhibit a layered macrostructure with wavy interfaces, aligned parallel to material flow during compression. Post-synthesis isothermal annealing at 1000 °C for 3 h promoted further phase transformations, enhancing mechanical properties including microhardness (up to 7.4 GPa), Young’s modulus (up to 200 GPa) and elastic recovery (up to 31.8%). X-ray powder diffraction, SEM, and EDS analyses confirmed solid-state diffusion as the primary mechanism for element interaction during synthesis and annealing. The developed materials show promise as PVD targets for depositing heat-resistant coatings. © 2025 by the authors.