Magnesium aluminate-based materials were prepared by applying different methods: (i) mechanochemical milling of the initial mixture of magnesium and aluminium nitrate powders (in appropriate stoichiometric amounts) followed by heat treatment at temperatures of 650°C and 850°C and (ii) melting of the mixture of nitrate precursors at 240°C followed by thermal treatment at 650°C, 750°C and 850°C. The effect of synthesis method on the structure and morphology of the obtained solids was studied by using various techniques such as: nitrogen adsorption-desorption isotherms, powder XRD, IR spectroscopy and SEM. It was shown that the mechanochemical milling performed before calcination procedure leads to obtaining of nanocrystalline magnesium aluminate spinel phase at lower temperature of 650°C in comparison with the method using thermal treatment only (at 750°C). The obtained nanomaterials exhibit mesoporous structure.