A series of Ti-B-(N) coatings prepared by de magnetron sputtering using TiB2 targets in Ar/N-2 gas mixtures has been chemically and structurally characterized by transmission electron microscopy, X-ray diffraction, electron energy-loss spectroscopy, and X-ray photoelectron spectroscopy. The influence of synthesis parameters such as applied heating power and nitrogen flow on the structure and chemical composition of the coatings has been studied. Independently of the experimental conditions employed during the synthesis, hexagonal TiB2 is the main crystalline phase present in the coatings. The use of N-2 leads to the formation of an amorphous mixture of BN/TiN phases, as well as a diminution of the TiB2 crystalline phase. The influence of the composition and structure of the coatings on their hardness is also discussed. (c) 2006 Elsevier B.V. All rights reserved.