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.