A coating suitable for use as protective oxide-forming coatings on Nb-based substrates, and particularly monolithic niobium-based alloys, exposed to high temperatures and oxidative environments. The coating contains aluminum, may further contain silicon, and optionally contains niobium, titanium, hafnium, and/or chromium, which in combination form one or more intermetallic phases that promote the formation of a slow-growing oxide scale. The intermetallic phases may be M(Al,Si)3, M5(Al,Si)3, and/or M3Si5Al2 where M is niobium, titanium, hafnium, and/or chromium.