Preparation methods are essential for the synthesis of materials with diverse structures, which may lead to the different physicochemical properties. The activities of catalysts for volatile organic compounds (VOCs) combustion can be improved by optimizing the preparation methods. In this paper, a novel ammonium bicarbonate pyrolysis method is successfully applied to prepare Co3O4 catalyst (Co3O4‐A), which is not only facile in preparation, but also superior to the Co3O4 catalysts prepared by the hydrothermal, sol‐gel, MOFs pyrolysis and carbonate pyrolysis method in the performance of chlorobenzene catalytic oxidation with 90 % conversion and mineralization temperature at 310 and 325 °C, respectively (1000 ppm CB, Air, WHSV=60,000 mL ⋅ g−1 ⋅ h−1). Furthermore, Co3O4‐A catalyst can maintain high catalytic activity for a long time, and has high tolerance to water vapor, which indicates Co3O4‐A catalyst has a good potential application value in catalytic combustion of chlorobenzene.