The applications and processing of nanostructured materials at high temperatures require stability of their morphology. However, in such environments (>1000 °C), these structures are prone to significant undesired microstructural changes that result in a loss of functional properties. The thermal stability of titania inverse opal films, prepared from self-assembled templates of monodisperse polystyrene spheres by infiltration utilizing atomic layer deposition and subsequent calcination, was assessed. Resistance to grain growth and a shift in the anatase-to-rutile transformation to higher temperatures was observed, with dramatic stability under vacuum. Vacuum annealed samples retained the anatase phase and exhibited minimal grain growth even after 3 h at 1300 °C. Photonic properties were retained until the transformation onset. The remarkable resistance was attributed to inhibition of surface diffusion and structure-substrate constraints. In addition to being technologically enabling, the results provide further insight into the titania system and its phase transformation mechanism.