High-temperature shape memory alloys are suitable materials for substituting hydraulic elements in the aerospace industry due to light weight and high reactive stresses developing during thermoelastic martensitic transformation and acceptable recoverable strain. These properties may be improved by plastic deformation; however, the plastic deformation of NiTiHf alloys along with structure investigation has yet to be studied systematically. Here, the hot deformation behavior of a NiTiHf alloy with hafnium content >20 at.% has been investigated, and the processing map has been elaborated according to the dynamic material model (DMM) based on the Prasad instability criterion. The deformation heating effect has been shown to affect the flow curves and accounts for profound softening during deformation due to quasi-adiabatic deformation mode at high strain rates. NiTiHf alloys have a much higher activation energy of plastic flow, and the instability region of plastic flow is much larger compared to binary NiTi alloys. Microstructural observations have revealed that in the instability regions, oxide bands and crack nucleation occur, whereas outside this region, such defects are not observed. Electron backscatter diffraction has demonstrated that at high temperatures and slow strain rates, discontinuous dynamic recrystallization occurs resulting in the necklace-type structure, while at high strain rates, this phenomenon has not been observed. Based on the obtained results, the preferable deformation conditions are established to be 850–1000 °C and 0.003–0.05 s−1.