Crystalline CNx/TiN multilayer composite coatings have been synthesized using an opposed cathode unbalanced magnetron sputtering system. Electron microscopy studies showed that the CNx/TiN coatings were fully crystalline and dense at small bilayer thicknesses. An amorphous phase was formed when the CNxlayer thickness exceeded 4–5 nm. Two newdspacings extracted by Fourier transform of digitized images of the crystalline CNxregion cannot be matched by known compounds formed by the detected elements. This provides limited evidence for the possible formation of a new carbon–nitrogen compound. Nanoindentation hardness about 45–55 GPa was reproducibly achieved for coatings produced under low nitrogen partial pressure and high substrate bias (−150 to −250 V). TiN (111) preferred orientation was strongly correlated to the high coating hardness. ©1996 American Institute of Physics.