The thermal behaviour of hydroxide mixtures aimed at Mg-AI spinel preparation is reported. The mixtures of hydroxides were prepared by precipitation reaction from Mg and A1 nitrate solutions, stoichiometrie to the spinel formation. Hydroxide mixtures with different phase distributions were investigated, prepared by varying the precipitation procedure. The results were related to the thermal behaviour of mechanical mixtures of separately precipitated hydroxides. The spinel formation was identified performing XRD analysis on powder samples heated at different temperatures. The coprecipitated mixtures are completely decomposed to spinel at 400~ The presence of the Mg-AI mixed hydroxide phase in the mixture is of primary concern to get spinel at low temperatures.