A MOF-templated method is developed to prepare bimetal oxide CuO/Co₃O₄ by in situ pyrolysis of Cu²⁺ partly-substituted ZIF-67 precursor. The physicochemical properties of CuO/Co₃O₄ are studied by various characterizations such as X-ray diffraction, Raman analysis, transmission electron microscope, scanning electron microscope, N₂ adsorption-desorption measurement, X-ray photoelectron spectroscope, O₂ temperature-programmed desorption, H₂ temperature-programmed reduction, etc. Comparison with CuO, Co₃O₄ and Mix-CuO/Co₃O₄, 90 % of both toluene conversion and mineralization over CuO/Co₃O₄ are fulfilled at around 229 °C under the condition of 1000 ppm toluene and weight hour space velocity =20,000 mL/(g h), which is promoted more than 40 °C. The better catalytic performance of CuO/Co₃O₄ attributes to high mutual dispersion of two oxides, porous structure, lower temperature reducibility, abundant lattice defects, more active oxygen species, higher Co³⁺/Co²⁺ and O_latt/O_ads molar ratios. Meanwhile, CuO/Co₃O₄ exhibits a better catalytic stability at different conversions and a good tolerance to 10 vol.% of water vapour. The investigation of temperature-dependent active oxygen species and in-situ DRIFTS results reveal that toluene oxidation on CuO/Co₃O₄ obeys Mars van Krevelen mechanism.