A process for forming diffusion aluminide coatings on an uncoated surface of a substrate, without interdiffusing a sufficient amount of aluminum into a coating layer to adversely affect the coating growth potential and mechanical properties of said coating layer. A metal substrate is provided comprising an external surface and an internal passage therein defined by an internal surface, at least a portion of the external surface of the substrate being coated with a coating layer selected from the group consisting of β-NiAl-base, MCrAlX, a line-of-sight diffusion aluminide, a non-line-of-sight diffusion aluminide, a pack diffusion aluminide, and a slurry diffusion aluminide on said substrate. The metal substrate is subjected to an aluminum vapor phase deposition process.