Ozone is a ubiquitous pollutant and manganese dioxide (MnO2) has been widely used for ozone decomposition. However, the effect of MnO2 structure on ozone decomposition has never been investigated. Three tunnel-structure polymorphs, i.e., alpha-, beta- and gamma-MnO2 were prepared and characterized by BET, TEM, XRD, H-2-TPR, O-2-TPD, NH3-TPD, TGA-MS and XPS. The activity of three MnO2 polymorphs for ozone decomposition followed the order of alpha->gamma->beta-MnO2. The alpha-MnO2 owned the largest specific surface area and lowest average oxidation state of Mn. Furthermore, the adsorbed oxygen species on the surface of alpha-MnO2 were more easily reduced. In-situ Raman spectroscopy results showed that peroxide species formed during ozone decomposition, and over alpha-MnO2 they were more easily decomposed by increasing reaction temperature. It was found that the catalytic activity of MnO2 strongly depended on the density of oxygen vacancies. Accordingly, the ozone decomposition mechanism based on the involvement and recycling of oxygen vacancy (V-O) is proposed. The decomposition of peroxide species is a rate-limiting step. These findings are helpful for designing more effective catalyst for ozone removal. (C) 2016 Elsevier B.V. All rights reserved.