Three-dimensional ordered meso-macroporous La0.7Sr0.3Fe0.5Co0.5O3 (3DOM LSFCO)-supported Co3O4 catalysts were designed and prepared via a PMMA-templating strategy for the total oxidation of 1,2-dichloroethane (1,2-DCE). The physicochemical properties of all synthesized samples were characterized by XRD, FE-SEM, TEM, HAADF-STEM, low-temperature N-2 sorption, XPS, H-2-TPR, and in situ FT-IR. The introduction of Co3O4 increases the generation rate of oxygen vacancy, playing a crucial role in adsorption and activation of oxygen species. The special 3DOM structure of perovskite-type oxide promotes 1,2-DCE molecules to effectively and intimately contact with the surface adsorbed oxygen over supported catalysts and further accelerates the redox process. Compared with pure LSFCO, all the Co3O4 supported catalysts show superior catalytic performance with reaction rate increases from 5.53 x 10(-12) to 2.29 x 10(-11) mol g(-1) s(-1) and E. decreases from 74.7 to 22.610 mol(-1). Amongst, the 10Co(3)O(4)/3DOM LSFCO catalyst exhibits the best catalytic activity, highest resistance to chlorine poisoning and lowest by-products concentration because of the largest amount of surface adsorbed oxygen. CO2, CO, HCl, and Cl-2 are the main oxidation productions, while some typical reaction intermediates such as vinyl chloride, 1,1,2-trichloroethane and trichloroethylene are also observed, especially over the 3DOM LSFCO sample. Furthermore, the reaction mechanism of 1,2-DCE oxidation over obtained catalysts was proposed based on the results of gas chromatography, in situ FT-IR, and on-line MS. It is believed that the Co3O4/3DOM LSFCO are promising catalysts for the total removal of chlorinated volatile organic compounds.