O-2 activation for the green conversion of chemicals has attracted a great deal of attentions in the field of chemistry. Developing catalysts for aerobic oxidation with both prominent instinct activity and desirable micro/nanostructure remains a tough challenge. In this work, hierarchical hollow Co-Ni-Mo-O mixed metallic-oxide nanotubes constructed by ultrathin CoMoO4/NiMoO4 nanosheets were fabricated using a sacrificial template method and employed as catalysts in aerobic oxidative desulfurization (AODS) of a model fuel. With air as the oxygen source, the catalyst demonstrated surprisingly high activity by achieving complete conversion of dibenzothiophene under mild reaction conditions. Besides, the catalyst demonstrated excellent stability on continuous repeated use. A further mechanism study reveals the electron coordination and transfer between different metal species as well as the activation route of O-2. Based on the above-mentioned results, the catalyst which allows a good exposure of metal centers, a high concentration of oxygen vacancies, and the desired electronic structure is expected to serve as the high-performance AODS catalyst.