This paper is aimed at understanding the tribo-oxidation of a physical vapor-deposited TiN coating when sliding against a corundum ball. This is achieved through a compositional and structural analysis of the wear debris. Wear debris particles generated at three different sliding speeds were analyzed with micro-Raman spectroscopy, transmission electron microscopy, and electron probe microanalysis. The analysis showed that the wear debris when formed at the low and medium sliding speed consist of TiO2 with a nanocrystalline structure containing both anatase and rutile structural elements. Only rutile structural elements could be observed in the debris formed at the high sliding speed. These results on the characterization of the wear debris are interpreted with calculations of the flash temperature in the tribo-contact and with recent ball-on-disk results on the wear rate of TiN as a function of the sliding speed to propose a mechanistic view of the tribo-oxidation and wear process. The relation with previous and recent experimental results on the static oxidation of TiN is also given.