Within the wide family of shape memory alloys (SMAs), TiNi-based alloys are characterized by unique characteristics, with good workability in the martensite phase and good resistance to corrosion and fatigue. In the nearest future, TiNi-based SMAs are expected the second birth to begin regarding their practical application, especially in creating a new material generation showing enhanced characteristics for clinical goals. Such a kind of expectations is naturally supposed to make a search among alloying elements for TiNi-based SMAs, as well as studies of adjacent effects in order to improve material properties. The objective of the work is to investigate the effect of heat treatment on the structure and properties of the quaternary Ti50Ni47.7Mo0.3V2 SMA, as potentially promising for medical devices. Specimens were prepared and annealed at 723, 923, 1123 K for 1 h. It was found that the studied alloy was in a multiphase state: TiNi-based intermetallic in three crystallographic modifications (austenite B2-phase and martensitic R- and B19¢structures) and secondary Ti2Ni(V) phase. The increase of the annealing temperature doesn't affect the martensite transformation (MT) sequence B2«R«B19′, but leads to a growth in lattice parameter of the parent phase. The most remarkable effect on the studied alloy was at 723 K. Volume fraction of Ti2Ni(V) precipitates in the structure was also maximum. It owes their presence to the shift of the MT points toward the lower temperature range. The temperature vs resistivity r(T) curves show a characteristic shape, which is typical for TiNi-based SMAs with a two-step nature of the B2«R«B19′ MT.