A series of (HfN)1−x
, ceramics with x representing the starting powder blend compositions of 0.0, 18.8, 28.1, and 46.7 at.%, have been fabricated by vacuum plasma spraying. During the plasma spraying, the mixture lost approximately 25 at.% nitrogen facilitating the precipitation of metallic and metal-rich nitride phases. These specimens underwent static air oxidation exposure up to 1700 °C. In general, it was found that the addition of tantalum nitrides to the hafnium nitrides resulted in poorer oxidation behavior. However, the 18.8 at.% specimen deviated from this trend and had the lowest observed mass change. This specimen formed a dark-colored oxide scale, indexed as Hf6Ta2O17, which acted as a passivation layer. Within the scale, hafnium oxynitride phases were observed. A transformation pathway in forming these rhombohedral oxynitride phases is proposed by the filling in of oxygen in the light element interstitial locations of the rhombohedral ε-Hf3N2 and ζ-Hf4N3 structures.