A thermal barrier coating system and a method for forming the coating system on a component designed for use in a hostile thermal environment, such as superalloy turbine, combustor and augmentor components of a gas turbine engine. The method is particularly directed to a thermal barrier coating system that includes a thermal insulating ceramic layer and a diffusion aluminide bond coat on which an aluminum oxide scale is grown to protect the underlying surface of the component and to chemically bond the ceramic layer. The bond coat is formed to contain an additive metal of platinum, palladium, rhodium, chromium and/or silicon, and an additive element of yttrium and/or zirconium, with possible additions of hafnium. The bond coat may be formed by codepositing aluminum with the active element, or by depositing the additive metal and active element on the surface of the component, and then aluminizing to form the diffusion aluminide bond coat.