We propose in this manuscript a new peroxo-mediated procedure for preparing magnesia-zirconia mixed oxides, with Mg/Zr molar ratio between 1 and 3, with enhanced distribution of basic sites. The mixed magnesia-zirconia oxides have been prepared from the gelled complex by Pechini-type method. The MgO-ZrO2 materials have been characterized and used as catalysts for acetone aldol condensation. The proposed preparation method provides a high degree of molecular homogeneity and favours the formation of magnesia-stabilized zirconia phase. Acetone gas-phase self-condensation was carried out over these catalysts as model reaction requiring the presence of basic sites. The condensation yields diacetone alcohol and mesityl oxide as mean C6 products, and phorones, isophorones and mesitylene as C9 products. In comparison to Mg-Zr oxide prepared by co-precipitation, these new materials present better conversions and higher selectivity to linear dimers and trimers (as mesitylene), whereas the selectivity for isophorones is significantly lower. (C) 2014 Elsevier B.V. All rights reserved.