The structural and chemical characterization of the TiC/rutile interface that grows in the high-temperature and low-oxygen partial pressure oxidation of TiC single crystals is reported. Based on previous data of micro-Raman and Auger electron spectroscopy (AES)-scanning electron microscopy (SEM) profiles of the TiC/rutile interface cross-section, a Ti oxycarbide phase is expected to form at the TiC/rutile interface. In order to be consistent with the above mentioned data, Ti oxycarbide should form by partial substitution of C with O without producing any change in the rock-salt structure of TiC except to small changes in the lattice parameter. Following the Ti oxycarbide e-gun synthesis by X-ray diffraction (XRD) analysis, the enhancement of the O substitution in the C sublattice of TiC has been shown. The final product has been identified,by chemical analysis as Ti1.00 +/- C-0.01(0.49) (+/-) O-0.01(0.4) (+/-) (0.1) having a XRD spectrum almost identical to TiC with a relative change of the lattice parameter equal to - 0.8%. This result confirms the reason why no other signals other than the signals of amorphous carbon and rutile appear in the micro-Raman profiles of the TiC/TiO2 interface as well as the reliability of the oxidation mechanism elsewhere proposed. (C) 2004 Elsevier B.V. All rights reserved.