The microwave-assisted combustion synthesis as a route to obtain ultrafine α-alumina and magnesium aluminate composite powders starting from the ammonium aluminum carbonate hydroxide precursor was investigated. The synthetic temperature and the crystallite size of the α- alumina nanocomposite powder were significantly affected by the environmental atmosphere in the microwave assisted combustion. The α-alumina and spinel composite powder was obtained by the microwave-assisted combustion at temperature of 1000°C under H2/N2, but at 1150°C by the normal heat process under air. The rapid transformation from γ- to α-phase was achieved by microwave assisted nucleation at low temperature of 900°C under H2/N2 atmosphere. The least crystallite size of 26.2 nm was obtained under H2/N2 atmosphere at 1000°C for 10 min.