The Co3O4 catalysts with different precursors (Na2CO3, CH4N2O) were synthesized and evaluated for its o-xylene catalytic oxidation performance. A series of techniques including BET, XRD, TEM, XPS, H2-TPR were employed to characterize the physical and chemical properties of catalysts under various preparation conditions. The results indicated that physisorption played an important role in the o-xylene removal and higher calcination temperature destructed the specific surface areas of the Co3O4 samples. The enhanced catalytic performance of Co3O4[sbnd]N catalyst was mainly attributed to be abundance in active Co3+ and lattice oxygen species, while that of Co3O4[sbnd]C catalyst was ascribed to the formation of superoxide anion, especially the lower calcination temperature facilitated the generation of active species. In addition, the reaction mechanisms toward o-xylene oxidation over Co3O4 catalysts obtained by different preparation methods were explored in detail. The o-xylene molecule preferentially adsorbed onto the Co3+ ion sites, and was further oxidized by the lattice oxygen or superoxide anion with the product being o-methyl benzyl alcohol. Soon the benzyl alcohol was transformed into the o-methyl benzaldehyde, and afterward to form benzoic acid. Later, the benzoic acid was converted into small-molecule carboxylate for Co3O4[sbnd]N catalyst, whereas for Co3O4[sbnd]C catalysts, the benzoic acid was further turned into maleic acid subsequently into acetone. Finally, both the small-molecule carboxylate and acetone species were oxidized to CO2 and H2O. This finding offers some valuable insights for designing efficient o-xylene oxidation catalysts and mitigating industrial air pollution. © 2025 Elsevier B.V.