Refractory materials hold great promise to develop functional multilayer coating for extreme environments and temperature applications but require high temperature and complex synthesis to overcome their strong atomic bonding and form a multilayer structure. Here, a spontaneous reaction producing sophisticated multilayer refractory carbide coatings on carbon fiber (CF) is reported. This approach utilizes a relatively low-temperature (950 °C) molten-salt process for forming refractory carbides. The reaction of titanium (Ti), chromium (Cr), and CF yields a complex, high-quality multilayer carbide coating composed of 1) Cr carbide (Cr3C2), 2) Ti carbide, and 3) Cr3C2 layers. The layered sequence arises from a difference in metal dissolutions, reactions, and diffusion rates in the salt media. The multilayer-coated CFs act as a permeable oxidation barrier with no crystalline degradation of the CFs after extreme temperature (1,200 °C) and environment (oxyacetylene flame) exposure. The synthesis of high-quality multilayer refractory coating in a fast, efficient, easy, and clean manner may answer the need for industrial applications that develop cheap and reliable extreme environment protection barriers.