Many nitrides, particularly BN and TiN, have stimulated commercial interest because of their extreme hardness, wear and corrosion resistance, and thermal and electrical properties. All of these features are enhanced by the resulting structures and the large degree of covalency exhibited by the metal-nitride bonds. Coatings of select nitrides with films of related materials may particularly influence these properties in critical surface and interface regions. Materials of interest include the deposition by plasma vapor deposition of Ti and TiN on BN substrates. Some of these systems were then subjected to varying degrees of physical and thermal alteration. Resulting structural and morphological features have been investigated with electron microscopy and x-ray diffraction. Critical importance is also attributed to the chemical behavior of species deposited and grown at the resulting interfaces. Detailed x-ray photoelectron spectroscopy has, therefore, been rendered of these interfaces using cross-sectional display and sputter etching. Movement of nitridation and interference from oxidation and carbide formation are of particular concern.