The paper presents the results concerning the combustion synthesis of spinel MgAl2O4 powder by using Mg(NO3)2, Al(NO3)3 and fuel mixtures. The rational selection of the fuel mixture: urea (U), glycine (G), β-alanine (β-A), monoethanolamine (MEA), triethanolamine (TEA), enables the formation of MgAl2O4 directly from the combustion reaction initiated at approximately 300°C; subsequent thermal treatments are no longer required. Surface area of the resulted spinel powders may be adjusted in a wide range, between 9 m2/g and 207 m2/g, by changing the nature and the ratio of the selected fuels from the mixture.