The morphology and surface characteristics of SCS(Solution Combustion Synthesis)-derived Ni–NiO nanocatalysts were studied. The ΤΕΜ results highlighted that the nanomaterial’s microstructure was modified by changing the reactants’ concentrations. The dendrites’ growth conditions were the main factors responsible for the observed changes in the nanomaterials’ crystallite size. Infrared camera measurements demonstrated a new type of combustion through dendrites. The XPS analysis revealed that the NiO structure resulted in the bridging of the oxygen structure that acted as an inhibitor of hydrogen adsorption on the catalytic surface and, consequently, the activity reduction. The RF-IGC indicated three different kinds of active sites with different energies of adsorption on the fresh catalyst and only one type on the aged catalyst. Aging of the nanomaterial was associated with changes in the microstructure of its surface by a gradual change in the chemical composition of the active centers.