Introduction. Development of Ni-Al intermetallic compounds is one of the priority directions of modern machine building. Due to such characteristics as high heat resistance, high temperature strength, and low density, nickel aluminides are used as functional coatings in the aerospace industry. The main methods of Ni-Al coating surfacing are High-Velocity Oxygen-Fuel and High-Velocity Air-Fuel spraying (HVOF and HVAF), atmospheric plasma spraying (APS) and its modification such as High-Velocity Atmospheric Plasma spraying (HV-APS) which provides non-equilibrium cooling conditions. Since there are eight different intermetallic compounds, as well as martensite transformation, Ni-Al coatings is quite interesting to study. The work purpose is to study the features of the martensitic structure in HV-APS coatings, and also to establish the effect of heating temperature on its decomposition. Materials and methods. Ni-Al coatings were surfaced onto a low-carbon steel substrate using the HV-APS method. Studies of the fine structure of the coatings were carried out using transmission electron microscopy (TEM). In addition, the influence heating temperature on structural transformations of the coatings was analyzed. Results and discussion. Two types of particles are formed in HV-APS coatings: with a dendritic and granular structure. The most part of HV-APS coatings consists of particles with a two-phase grain structure (NiхAl1-х and γ'-Ni3Al grains). Only NiхAl1-x grains undergo martensitic transformation at cooling. Martensite in large grains (sizes greater than 500 nm) has a lamellar structure, while small grains are completely transformed into one martensite plate. In addition, the coatings contain grains in which martensite plates (NiхAl1-х) and β-phases alternated. It is shown the behavior of martensitic plates at colliding with each other, as well as with the γ′-Ni3Al grain. Heating up to 400 °C contribute the begins of martensite decomposition in individual grains with the release of a secondary phase; after heating up to 600 °C all martensite dissolves.