A series of Ni-Mg-Al hydrotalcite-derived mixed metal oxides with different Ni/Mg ratios were prepared by the coprecipitation method followed by calcination at 600 °C. The hydrotalcite-like materials, as well as their calcined forms, were characterized with respect to structure (XRD, UV-Vis DRS), chemical composition (ICP-OES), textural parameters (low-temperature sorption), dispersion of nickel species (-chemisorption) and nickel species reducibility (-TPR). Moreover, the process of hydrotalcite-like materials’ thermal transformation to mixed metal oxide systems in air and argon flow was studied by the TG-DTA method. The activity of the studied catalysts in the reaction of ammonia decomposition increased with an increase in nickel content in the samples. It was shown that nickel species incorporated into the Mg-Al oxide matrix segregated under conditions of reduction in a flow of mixture with the formation of metallic nickel crystallites of the average size of about 10 nm. The size of nickel crystallites was practically no change in the subsequent reduction cycles and resulted in increased catalytic activity in comparison to larger crystallites of metallic nickel (20.2–23.6 nm) deposited on and MgO.