The role of defect and transport properties of transition metal sulfides on the kinetics and mechanism of high-temperature sulfide corrosion of metals and alloys is discussed. It has been shown, that due to the very high concentration of defects in common metal sulfides, not only pure metals but also conventional high-temperature alloys (chromia and alumina formers) undergo very rapid degradation in highly sulfidizing environments. Refractory metals, on the other hand, are highly resistant to sulfide corrosion, their sulfidation rates being comparable with the oxidation rate of chromium. Pioneering work of Douglasset al. has shown that alloying of common metals by niobium or molybdenum, and in particular combined alloying by molybdenumand aluminum, dramatically decreases the sulfidation rate. A novel Fe−30Mo−9Al alloy has been proved to be highly resistant to sulfide corrosion, its sulfidation rate being comparable with that of pure molybdenum. Even better resistance to highly-sulfidizing environments show new amorphous Al−Mo and Al−Mo−Si alloys, these materials also being simultaneously oxidation resistant. Thus, new prospects have been created for the development of a new generation of coating materials, resistant to multicomponent sulfidizing-oxidizing atmospheres, often encountered in many branches of modern technology.