An overlay coating for articles used in hostile thermal environments. The coating has a predominantly gamma prime-phase nickel aluminide (Ni3Al) composition suitable for use as an environmental coating and as a bond coat for a thermal barrier coating. The coating has a composition of, by weight, at least 6% to about 15% aluminum, about 2% to about 5% chromium, optionally one or more reactive elements in individual or combined amounts of up to 4%, optionally up to 2% silicon, optionally up to 60% of at least one platinum group metal, and the balance essentially nickel. A thermal-insulating ceramic layer may be deposited on the coating.