Highly toxici and reactive chlorinated VOCs (Cl-VOCs) is urgent for purification by the most favoured catalytic oxidation, however, the formation of polycholoriated byproducts is hugely obstacle. Here, monoclinic and 3D urchin-like CePO4 was synthesized and used as the support of highly active but lowly selective Co3O4 for catalytic oxidation of Cl-VOCs. The prepared Co3O4/CePO4 using ascorbic acid as a chelating agent presented a high activity and low selectivity of vinyl chloride (VC) for catalytic oxidation of 1,2-dichloroethane (DCE) due to the high dispersion of Co3O4, some possible polychlorinated byproducts were completely inhibited in the presence of CePO4. The co-introduction of RuO2 further suppressed the formation of VC owing to the enhanced redox ability and migration of surface lattice oxygen. Moreover, RuCoOx/CePO4 also revealed the superior versatility, durability and thermal stability as well as the outstanding resistance to CO2, H2O and sulfur.