In modern materials science, a considerable amount of research is focused on obtaining new ceramic materials to create efficient functional elements. Acquiring highly efficient and highly stable ceramic catalysts for alternative energy is an important task that demands an urgent solution. Addressing this issue promptly is essential as it will facilitate the development of new technologies that can prevent future energy crises. Nickel oxide NiO or spinels of NiAl2O4 composition are excellent candidates as high temperature catalysts used in alternative energy applications. This paper studies the synthesis of NiO/NiAl2O4 composite ceramics and the effect of high-temperature aging on their phase composition, crystalline properties, and dielectric characteristics. The study found that the phase composition and microstructure of the ceramics are unchanged by thermal aging (aged at 700 °C), while the crystalline parameters and low-frequency dielectric characteristics may undergo significant changes over time, exhibiting notable fluctuations depending on the duration of aging. The observed variations were predominantly influenced by the microstructural features of the composite ceramics. As the average grain size increased and the phase transformations were completed, the crystalline parameters and low-frequency dielectric characteristics reached a stable state without further alteration. For NiO/NiAl2O4 ceramics with a sintering temperature of 1500 °C, the highest shrinkage, low dielectric loss values and acceptable hardness were observed, indicating that the fabricated ceramics are suitable for mechanical processing. In general, the obtained composite ceramics show high temperature stability and are ready for use in hydrogen energy applications as functional elements.