The paper examines the phase composition, structure, and properties of AlN-MoSi2 alloys and associated electrospark-deposited coatings on titanium. It is shown that the most intensive erosion and mass transfer are characteristic of alloys containing 60–80 wt.% MoSi2 and that the erosive characteristics essentially depend on the electrospark treatment parameters. A protective coating with a thickness of 30–40 µm and hardness to 1 GPa is formed on the substrate. There is a thermal impact area up to 300 µm deep and 1.4 GPa hard under the coating. The high-temperature holding of coated samples promotes the rapid formation of heat-resistance phases in the coating and the formation of a secondary structure in the thermal impact area. As a result, this area becomes thicker and the hardness of its material increases up to 1.9 GPa.