© 2019 Elsevier Inc. The surface/subsurface characterization of chromium nitride (CrN)/silicon nitride (Si3N4) sliding contact was carried out, to comprehend how the composition migration and structural transformation across the dynamically-formed tribo-interface evolve with the varying temperature. Superior wear and friction performance is achieved for the chromium nitride (CrN)/silicon nitride (Si3N4) contact at 800 °C. The tribo-interface demonstrates two structural characteristics, a superficially disordered nano-scale grained tribofilm and an underlying deformed coarse-grained layer, being temperature-dependent. The unique multilayered structure and oxides segregation at the sliding interface are responsible for the adaptive capability of the rubbing contact during their interaction with oxygen/air at 800 °C. The computational analysis based on the Density Functional theory (DFT) was further implemented to confirm the tribochemical interaction of predominant oxide heterogeneities.