Early transition metal carbides are considered to be superior candidate materials for oxidizing environments at temperatures exceeding 2000 degrees C. Generally, the remarkable oxidation resistance is largely attributed to a carbonaceous oxide interlayer (eg, Hf-O-C, Zr-O-C, and Ta-O-C), located at the interface between the external oxide layer and internal carbide (eg, HfC, ZrC, and TaC), acting as the primary oxygen barrier. However, the oxygen barrier mechanism of the carbonaceous oxide interlayer remains unclear. Herein, through studying the oxidation behavior of a novel multicomponent carbide Hf0.5Zr0.3Ti0.2C in oxidizing environments up to 2500 degrees C, the oxygen barrier mechanism of the carbonaceous oxide was recently revealed. We found that the oxygen barrier resulted from the slow oxygen diffusion through the inner grains of Hf-Zr-Ti-O due to the presence of carbon formed at the grain boundaries because of the existence of compact external oxide layer, beneath which the Hf-Zr-Ti-O-C interlayer possesses much lower oxygen activity and temperature that allow carbon to exist stably. This as-formed carbon strongly retarded the fast diffusion of oxygen along the grain boundaries of oxides. Additionally, desirable synergisms of the designed multicomponent system, particularly, the outward short-circuit diffusion of Ti, lead to the self-healing of the external oxide layer, evidently enhancing integral protection performance against oxidizing environments.