A coating system for Si-containing materials, particularly those for articles exposed to high temperatures. The coating system exhibits improved resistance to corrosion from sea salt and CMAS as a result of using aluminate compounds to protect silicate-containing layers of the coating system. The coating system includes an environmental barrier coating, a thermal barrier coating overlying the environmental barrier coating and formed of a thermal-insulating material, and a transition layer between the environmental barrier coating and thermal barrier coating, wherein the transition layer contains at least one aluminate compound and/or alumina.