A process for generating highly porous α-Al2O3 ceramics has been developed. In this paper, a combination of self-assembly and atomic layer deposition is demonstrated as a means to fabricate inverse alumina opals, which have their structures transformed via sintering. The resulting highly porous structure is stable even after a 4 h dwell time at 1400 °C, in contrast to structures generated by conventional powder metallurgy, sol-gel or colloidal powder suspension infiltration methods. TEM analysis reveals that the structure consists of single grain domains of up to 3 μm, each containing a randomly interconnected network of alumina ligaments that share a common crystalline orientation, suggesting a different mechanism of grain boundary migration during sintering. These highly porous α-alumina ceramics are considered to be ideal for filtration or catalysis applications.