Co₃O₄, MgCo₂O₄ and MgO materials have been synthesized using a simple co-precipitation approach and systematically characterized. The total conversion of toluene to CO₂ and H₂O over spinel MgCo₂O₄ with wormlike morphology has been investigated. Compared with single metal oxides (Co₃O₄ and MgO), MgCo₂O₄ with the highest activity has exhibited almost 100% oxidation of toluene at 255 °C. The obtained results are analogous to typical precious metal supported catalysts. The activation energy of toluene over MgCo₂O₄ (38.5 kJ/mol) is found to be much lower than that of Co₃O₄ (68.9 kJ/mol) and MgO ((87.8 kJ/mol)). Compared with the single Co and Mg metal oxide, the as-prepared spinel MgCo₂O₄ exhibits a larger surface area, highest absorbed oxygen and more oxygen vacancies, thus highest mobility of oxygen species due to its good redox capability. Furthermore, the samples specific surface area, low-temperature reducibility and surface adsorbed oxygenated species ratio decreased as follows: MgCo₂O₄ > Co₃O₄ > MgO; which is completely in line with the catalytic performance trends and constitute the reasons for MgCo₂O₄ high excellent activity towards toluene total oxidation. The overall finding supported by ab initio molecular dynamics simulations of toluene oxidation on the Co₃O₄ and MgCo₂O₄ suggest that the catalytic process follows a Mars–van Krevelen mechanism.