For many high-temperature applications, coatings are applied in order to protect structural materials against a wide range of different environments: oxidation, metal dusting, sulphidation, molten salts, steam, etc. The resistance achieved by the use of different kind of coatings, such as functionally graded material coatings, has been optimized with the latest designs. In the case of supercritical steam turbines, many attempts have been made in terms of micro-structural coatings design, mainly based on aluminides, and other diffusion coating systems in order to consider alternatives, nano-structured coatings based on Cr and Al compositions and deposited by a physical vapor deposition technique, were assessed to high-temperature oxidation resistance in steam environments. The oxidation kinetics where analyzed for up to 2,000 h at 650 °C by means of gravimetric measurements. The evaporation behavior was also analyzed by thermogravimetric-mass spectrometry. Excellent results where observed for some of the nano-structured coatings tested. Those results where compared to results obtained for micro-structured coatings. Based on that comparison, it was deduced that the nano-structured coatings have a potential application as protective systems in high-temperature steam environments.