It was reported for the first time that carbon nanotubes (CNTs) as metal-free catalyst exhibited an excellent activity in the selective oxidation of ethylbenzene (EB) to acetophenone (AcPO) in the liquid-phase with oxygen as the oxidant. The reasonable mechanism responsible for the liquid-phase oxidation of EB on CNTs was proposed. The results demonstrated that the CNTs played an important role in the decomposition of 1-phenylethyl hydroperoxide (PEHP) and contributed to the production of AcPO, owing to π–π interactions between the radical species and peroxides and the graphene sheets of the CNTs. Surface carboxylic groups of the CNTs were unfavorable to EB oxidation. Adsorption energies of the radical species and peroxides on pristine and modified CNTs with carboxylic groups were calculated by DFT. These theoretical calculations were well consistent with the experimental results, and also supported the presented mechanistic pathway of EB oxidation on CNTs. This study not only presents a facile and effective alternative to cobalt-based catalysts for the selective oxidation of EB to AcPO but also gives new insight into the effect of surface structures on carbon-catalyzed reactions, and further pushes forward the research on carbon catalysis.