Catalytic oxidation of volatile organic compounds (VOCs) has been studied with cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) synthesized in buffer solutions. Characterization of OMS-2 has been done using X-ray diffraction (XRD), infrared (IR), thermogravimetric analysis–differential scanning calorimetry (TGA–DSC), combined temperature programmed decomposition and mass spectrometry (TPD–MS), adsorption and adsorbate IR techniques. OMS-2 was found to possess excellent hydrophobicity and strong affinity for VOCs. Excellent activity and stability of OMS-2 in oxidation of VOCs at relatively low temperatures (100% conversion of 0.9% C6H6 in air or 2.5% ethanol in air at 20 000 h−1 GHSV below 300°C) are due to these hydrophobic properties and to facile evolution of lattice oxygen without destroying the structure (120–650°C).