The investigation of step-by-step sampled products of mechanical alloying (MA) of two equimolar mixtures of TiC–VN and TiN–VN sintered with high-energy ball mill is conducted implicating number of methods of x-ray diffractometry (x-ray phase analysis, x-ray structural analysis, investigation of crystallite sizes and microstresses in the crystal lattice, etc.). As shown, the crystal structures of VN, TiN, and TiC undergo significant structural transformations during MA treatment. Specifically, part of the vanadium or titanium atoms migrate from their localization to tetrahedral pores under the impact load and part of those atoms leave their positions in the lattice and form separate clusters in the reaction zone of the milled powder. These processes lead to substantial accumulation of crystallographic point defects in phase structures presented by vacancies in metal sublattices of VN, TiN, TiC and substitutional atoms of vanadium or titanium in the crystal lattice. Overall, the increase of the portion of mentioned point defects is accompanied by the increase of microstresses in phases. Substantial portion of accumulated vacancies and some fraction of the vanadium- and titanium-atoms’ clusters formed in the reaction zone of the milled powder create preconditions for further formation of mutual solid substitutional alloys. As shown, the impact of the MA treatment is decreased in the VN → TiN → TiC series that can be explained with such phase characteristics as dissociation energy, elasticity modulus, and thermal conductivity. The MA-activated dispersed (crystallite size up to 20 nm) powder mixture of TiC–VN acquired in the work may be recommended as alloying additive for medical titanium composites to increase the functional characteristics.