An oxidation protection coating for metal substrate surfaces. The coating, according to a preferred embodiment, comprises an initial or first layer of a glass-ceramic, such as a barium aluminosilicate composed chiefly of baria, silica and alumina; or mullite, composed of silica-alumina or, alternatively, baria-silica. Titanium dioxide, nickel oxide or SnO.sub.2 can be added. The next layer of the coating is comprised of alumina or silicon carbide. The third or final layer is comprised of a thin layer of silica or a high-silica material, e.g., a silica containing 4% B.sub.2 O.sub.3. For a thicker third layer, particles of a dark solid, such as boron silicide, ferrous oxide, ferric oxide, nickel oxide, manganese dioxide, carbon or silicon carbide, can be incorporated. The three-layer coating provides high emittance and low catalytic activity for the recombination of oxygen and nitrogen, as well as being a hydrogen diffusion barrier.