Nanoporous and nanostructured materials are becoming increasingly important for advanced applications involving, for example, bioactive materials, catalytic materials, energy storage and conversion materials, photonic crystals, membranes, and more. As such, they are exposed to a variety of harsh environments and often experience detrimental morphological changes as a result. This article highlights material limitations and recent advances in porous materials-three-dimensionally ordered macroporous (3DOM) materials in particular-under reactive or high-temperature conditions. Examples include systems where morphological changes are desired and systems that require an increased retention of structure, surface area, and overall material integrity during synthesis and processing. Structural modifications, changes in composition, and alternate synthesis routes are explored and discussed. Improvements in thermal or structural stability have been achieved by the isolation of nanoparticles in porous structures through spatial separation, by confinement in a more thermally stable host, by the application of a protective surface or an adhesive interlayer, by alloy or solid solution formation, and by doping to induce solute drag.