AbstractMacroporous structures are of interest for several technological applications such as catalysis, sensors, filters, membranes, batteries, energy conversion devices, structural colors, and reflective thermal barrier coatings. Ceramic-based inverse opal macroporous structures are especially interesting for high-temperature applications. However, the interrelation between the structural parameters, mechanical properties, and thermal stability of such structures is not yet clarified. In this work, we analyzed the mechanical properties as well as the thermal stability of aluminum oxide inverse opal three-dimensional macroporous structures with different macropore sizes and shell thicknesses produced by atomic layer deposition. Our results show that the structures’ thermal stability increased with increasing shell thickness and macropore size, however, their higher stability was not linked to their mechanical properties. To be able to explain this unexpected behavior, finite element modeling simulations were performed, showing that bending stresses became more pronounced with increasing shell thickness, potentially creating additional critical sites for crack initiation and consequent structural failure.