A novel redox-precipitation method was developed for the preparation of alpha-MnO2, where Mn(NO3)(2) and KOH were titrated into excess KMnO4 solution at pH 8. For comparison, MnOx was also prepared using a conventional precipitation method. These materials were characterized by XRD, BET, SEM/EDS, XPS, and H-2-TPR techniques, and their catalytic activities were evaluated for the complete catalytic oxidation of a typical volatile organic compound (VOCs), o-xylene. The novel method produced open porous hierarchically structured microcrystalline alpha-MnO2 containing almost 100% Mn4+ ion on its surface. Whereas, the conventional precipitation method produced a mixture of MnO2 and Mn3O4 with a closely packed spherical morphology containing only 31% Mn4+ ion on its surface. It was found that alpha-MnO2 exhibited good low-temperature reducibility, and that it could convert 100% o-xylene into CO2 at 220 degrees C at a space velocity of 8000 h(-1), 50 degrees C lower than the MnOx prepared by the conventional method. The surface concentration of Mn4+ ion in alpha-MnO2 played a key role for its high catalytic activity for the complete oxidation of o-xylene. In addition, the open porous structure and the presence of small amount of potassium ion in the microcrystalline alpha-MnO2 channel may also be responsible for its excellent catalytic performance. Effects of pH and calcination temperature on its catalytic activity were investigated, and optimal preparation conditions were found. Durability of the alpha-MnO2 was also studied. (C) 2012 Elsevier B. V. All rights reserved.