AbstractEthyl acetate is one of typical volatile organic compounds (VOCs) emitting from solvent use, and removing ethyl acetate from exhaust air is vital to VOCs abatement. The mesoporous manganese oxide (MnOx) samples were sonochemically synthesized by the reduction of KMnO4 using Mn(NO3)2. The characterization shows that γ‐MnO2, β‐MnO2, and bixbyite‐like Mn2O3 were obtained by calcining the MnOx samples from 200°C to 500°C. The results show that γ‐MnO2 and β‐MnO2 possess more Mn4+ than bixbyite‐like Mn2O3. β‐MnO2 has the highest contents of surface oxygen species (Oads) and average oxidation state (AOS) among the MnOx catalysts. Based on a 7‐day test, β‐MnO2 performed the highest activity for the catalytic ozonation of ethyl acetate compared with the other MnOx catalysts. The results show that ethyl acetate is easy to be destroyed but difficult to be completely mineralized by catalytic ozonation. Lower gas hourly space velocity (GHSV) leads to higher CO2 selectivity and more intermediate products form in the catalytic ozonation of ethyl acetate under higher GHSV. A further study indicates that β‐MnO2 has a long‐term stability for catalytic ozonation of ethyl acetate because the accumulation and the decomposition of intermediate products are in a dynamic equilibrium during the catalytic ozonation.