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Abstract Alloy of the V-Ti-Cr system is a promising material exploited under high radiation and in corrosion environment. We sintered V-4.9Ti-4.8Cr alloy from particles with original average size of 30, 280 and 200 μm, respectively for vanadium, titanium and chromium powders, by pressing of the powder mixture and its further sintering. The studies were undertaken using the methods of X-ray structural analysis, scanning electron microscopy with an energy dispersive analyzer and transmission electron microscopy. It was established that the structure of the alloy represented matrix grains (BCC solid solution), along the boundaries and at junctions of which the groups of oxycarbonitride particles of V, Ti, Cr (C,N,O) type of the variable elemental composition were arranged. The particles possessed a plate-like (0.4 x 2.0 μm) and rounded (0.5 μm) shape. The solid solution of the alloy was heterogeneous by concentration. This was evidenced by the complications of the diffraction patterns obtained from the corresponding sections of the structure. These were cords of main reflexes, satellites and emergence of a moire banded contrast in separate sections of the sample. Inside the matrix grains, there were nanoparticles (15 μm) of carbide V55Cr25C20, being a source of elastic internal local stresses.