Developing efficacious catalysts with superior Cl resistance and polychlorinated byproduct inhibition capability is crucial for realizing the environmentally friendly purification of chlorinated volatile organic compounds (CVOCs). Activating CVOC molecules and desorbing Cl species by modulating the metal−oxygen property is a promising strategy to fulfill these. Herein, a bifunctional CoRu/Al 2 O 3 catalyst with synergistic Co and Ru interactions (Ru−O−Co species) was rationally fabricated, which possesses abundant surface Co 2+ and Ru δ+ sites and collaboratively facilitates the activation of lattice oxygen (O 2− ) and molecular oxygen (O 2 → O 2− → O − ), accelerating 1,2dichloroethane (1,2-DCE) decomposition via the reaction route of enolic species → aldehydes → carboxylate/carbonate. Furthermore, CoRu/Al 2 O 3 stimulates 1,2-DCE oxidation under humid conditions as H 2 O molecules can be easily activated to active *OH (potential oxidizing agent) over Ru species, accelerating C−Cl dissociation and Cl desorption and promoting the transformation of catecholate-type (C�O) species to easily oxidizable carboxylic acid (COOH) species, remarkably suppressing the formation of hazardous CCl 4 and CHCl 2 CH 2 Cl. This study provides critical insights into the development of bifunctional catalysts to synergistically activate surface oxygen species and H 2 O molecules for industrial CVOC stable and efficient elimination.