Abstract: A thermal barrier coating and a method for forming the coating on an article designed for use in a hostile thermal environment, such as turbine, combustor and augmentor components of a gas turbine engine. The method is particularly directed to increasing the spallation resistance of a thermal barrier coating system that includes a thermal insulating ceramic layer. The coating system of this invention generally includes a nickel aluminide alloy on which an aluminum oxide layer is formed, over which a ceramic layer is deposited so as to overlie and contact the aluminum oxide layer. The coating system does not include a bond coat, such as a diffusion aluminide or MCrAlY coating known in the prior art. The nickel aluminide alloy may be a binary NiAl alloy consisting essentially of nickel and aluminum in stoichiometric amounts, or may contain one or more oxygen-active elements.