The effect of the initial phase composition of a Ti–Al–V–Mo alloy (VT16 according to Russian classification) on the evolution of its structural-phase state during the formation of ultrafine-grained structure and subsequent annealing is investigated by methods of optical and transmission electron microscopy and x-ray diffraction analysis. The structure is produced by cyclic pressing with a change of the deformation axis in each cycle combined with a gradual decrease of the pressing temperature from 1073 to 723 K. As this takes place, α″ → α + β and β → α phase transitions are found to develop in the test alloy. The phase state of the ultrafinegrained material thus produced depends for the most part on its elemental composition and severe plastic deformation regime. Annealing below the recrystallization temperature is shown to give rise to a β→α phase transition and alloying element redistribution. The foregoing processes allow for retaining a high level of the strength properties of the alloy.