Manganese oxides having 2 × 2 tunnel structures (cryptomelanes) have been synthesized by a milling method in order to test their efficiency as catalysts for the abatement of volatile organic compounds, using toluene as probe molecule. These materials present excellent textural properties, arising from the nanofiber morphology and were active for toluene total oxidation. DRIFTS of the adsorbed phase allow proposing the role of lattice oxygen in the catalytic reaction.