Nowadays, the treatment of ozone has become critically important due to the health risks caused by even minimal amount of ozone in the ambient air. In this work, LaFeO3 doped with Mg, Ca, Sr and Ce on A-site are synthesized by sol-gel method and adopted as a highly active ozone decomposition catalyst. The results show that the Ce doped LaFeO3 exhibits the highest catalytic activity with the optimal doping concentration marked as La0.5Ce0.5FeO3. It reaches high conversion efficiency of 97 % and 90 % to 1000 ppm ozone at high weight hourly space velocity of 720,000 and 1440,000 mL g−1 h−1, which is one of the highest in the literature. The distortion of [FeO6] octahedra reached the maximum when the doping amount of Ce was 0.5 as revealed by X-ray diffraction and Rietveld fitting. The high ozone catalytic activity could be assigned to the easy electron loss from eg orbit caused by high crystal field splitting energy, abundant oxygen vacancies resulting from the biggest distortion of [FeO6] octahedra and quick transfer between Fe2+ and Fe3+.