Small additions of Hf to NiAl produce a significant increase in the high-temperature strength of single crystals. Hf has a very limited solubility in NiAl and in the presence of Si, results in a high density of G-phase (Ni16Hf6Si7) cuboidal precipitates and some G-platelets in a NiAl matrix. These precipitates have a F.C.C structure and nucleate on {100}NiAl planes with almost perfect coherency and a cube-on-cube orientation-relationship (O.R.). However, G-phase is metastable and after prolonged aging at high temperature dissolves at the expense of a more stable Heusler (β'-Ni2AlHf) phase. In addition to these two phases, a third phase was shown to be present in a NiAl-0.3at. % Hf alloy, but was not previously identified (Fig. 4 of ref. 2 ). In this work, we report the morphology, crystal-structure, O.R., and stability of this unknown phase, which were determined using conventional and analytical transmission electron microscopy (TEM).Single crystals of NiAl containing 0.5at. % Hf were grown by a Bridgman technique. Chemical analysis indicated that these crystals also contained Si, which was not an intentional alloying addition but was picked up from the shell mold during directional solidification.