Articles having coatings that are resistant to high temperature degradation are described, along with methods for making such articles. The article comprises a coating disposed on a substrate. The coating comprises a plurality of elongated surface-connected voids. The article further includes a protective agent disposed within at least some of the voids of the coating; the protective agent comprises a substance capable of chemically reacting with liquid nominal CMAS to form a solid crystalline product outside the crystallization field of said nominal CMAS. This solid crystalline product has a melting temperature greater than about 1200 degrees Celsius. The method generally includes disposing the protective agent noted above within the surface connected voids of the coating at an effective concentration to substantially prevent incursion of CMAS materials into the voids in which the protective agent is disposed.