Abstract A series of mixed oxides (Mn‐Mg‐Al) is prepared by coprecipitation via a hydrotalcite route with different manganese ratios. Structural, textural, and redox properties are studied by XRD, N 2 ‐sorption, H 2 ‐TPR, and XPS techniques. Mn x Mg 6‐x Al 2 ‐O mixed oxides (with 0≤x≤6) are tested in the total oxidation of ethanol and toluene, two probe molecules representing respectively oxygenated and aromatic VOCs. Catalysts with higher manganese contents have shown the best catalytic performance for the oxidation of both ethanol and toluene. The surface activity of the materials is mainly related to the presence of manganese species in three different oxidation states (+II, +III, and +IV) in the bulk and on the material's surface. Since high Mn‐content catalysts showed similar physicochemical properties and catalytic activity, Mn 4 Mg 2 ‐O is selected as the optimal composition of these materials. Furthermore, its aging test is compared to that of noble metal‐based commercial catalysts (Pd/γ‐Al 2 O 3 ).