Nanostructured bulk NiAl materials were prepared at high pressure and temperature (0–5.0 GPa and 600–1500 °C, respectively). The sintered samples were characterized by x-ray diffraction, scanning electron microscope, density, and indentation hardness measurements. The results show that NiAl nanoparticles may have a compressed surface shell, which may be the reason why NiAl nanomaterials were difficult to densify sintering using conventional methods and why high-pressure sintering was an effective approach. We also observed that B2-structured NiAl could undergo a temperature-dependent phase transition and could be transformed into Al0.9Ni4.22 below 1000 °C for the first time. It is interesting to note that Vickers hardness decreased as grain size decreased below ∼30 nm, indicating that the inverse Hall-Petch effect may be observed in nano-polycrystalline NiAl (n-NiAl) samples. Moreover, a tentative interpretation was developed for high-pressure nanosintering, based on the shell-core model of nanoparticles.