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The direct decomposition of N2O was investigated over a series of magnesium cobaltite catalysts, MgxCo1-xCo2O4 (0.0 ≤x ≤ 1.0), which were prepared by the thermal decomposition of stoichiometric amounts of magnesium hydroxide and cobalt acetate. The thermal genesis of the different catalysts from their precursors was explored using thermogravimetric analysis, differential thermal analysis, and X-ray diffraction. Texture analysis was carried out using N2 adsorption at -196 ℃. We found that all the catalysts that were calcined at 500 ℃ have a spinel structure. N2O decomposition activity was found to increase with an increase in the spinel structures magnesium content. The influence of alkali cation promoters (Li, Na, K, and Cs) on the activity of the most active catalyst in the MgxCo1-xCo2O4 series, i.e. MgCo2O4, was also investigated. The sequence of the promotional effect was found to be: un-promoted 0.05, based on N2 adsorption and scanning electron microscopy results.