Enhancing the activity and stability of catalysts is a major challenge in scientific research nowadays. Previous studies showed that the generation of an additional pore system can influence the catalytic performance of porous catalysts regarding activity, selectivity, and stability. This study focuses on the epoxide-mediated sol-gel synthesis of mixed metal oxides, NiAl2O4 and CoAl2O4, with a spinel phase structure, a hierarchical pore structure, and Ni and Co contents of 3 to 33 mol % with respect to the total metal content. The sol-gel process is accompanied by a polymerization-induced phase separation to introduce an additional pore system. The obtained mixed metal oxides were characterized with regard to pore morphology, surface area, and formation of the spinel phase. The Brunauer-Emmett-Teller surface area ranges from 74 to 138 m2·g-1 and 25 to 94 m2·g-1 for Ni and Co, respectively. Diameters of the phase separation-based macropores were between 500 and 2000 nm, and the mesopore diameters were 10 nm for the Ni-based system and between 20 and 25 nm for the cobalt spinels. Furthermore, Ni-Al spinels with 4, 5, and 6 mol % Ni were investigated in the dry reforming of CH4 (DRM) with CO2 to produce H2 and CO. CH4 conversions near the thermodynamic equilibrium were observed depending on the Ni content and reaction temperature. The Ni catalysts were further compared to a noble metal-containing catalyst based on a spinel system showing comparable CH4 conversion and carbon selectivity in the DRM.