Inverse oxide/metal catalysts are recently employed and of great importance in catalytic oxidation reactions, due to the high activity and sintering-resistance. However, the investigations for identification of active-site structure, adsorption-activation of O2, and insight into interface-enhanced mechanism are relatively scare. Herein, the inverse “CoOx-Au” ensemble (∼10 nm CoOx nanoparticles onto ∼30 nm Au particles) for gas-phase alcohol oxidation was exampled to investigate above issues, under the premise of delivering 92 % benzyl alcohol conversion with 98 % benzaldehyde selectivity at 240 °C and atmospheric pressure. It is revealed that O2 is activated at CoOx-Au interface. The “CoO-Au ↔ Co3O4-Au” redox cycle at CoOx-Au interface proceeds over the “CoO↔Co3O4” cycle on CoOx surface, due to the weakened interfacial Co-O bond. And the enhanced redox cycle intensifies O2 activation and lattice O supply. The O2 activation at inverse oxide-metal interface provides promising clue for rational design of inverse catalysts for catalytic oxidation reactions.