•MnOx/biochar and FeOx/biochar significantly improved ozonization of ATZ.•Enhanced formation of •OH was observed in the catalytic ozonation systems.•Increased Lewis acid sites and electron transfer contributed for the O3 catalyzation.•Toxicity of ATZ had been largely eliminated after the heterogeneous catalytic ozonation. After reaction with permanganate or ferrate, the resulted Mn-loaded and Fe-loaded biochar (MnOx/biochar and FeOx/biochar) exhibited excellent catalytic ozonation activity. O3 (2.5 mg/L) eliminated 48% of atrazine (ATZ, 5 μM) within 30 min at pH 7.0, while under identical conditions, ozonation efficiency of ATZ increased to 83% and 100% in MnOx/biochar and FeOx/biochar (20 mg/L) heterogeneous catalytic systems, respectively. Radical scavenger experiment and electron paramagnetic resonance (EPR) analysis confirmed that hydroxyl radical (•OH) was the dominant oxidant. Total Lewis acid sites on MnOx/biochar and FeOx/biochar were 3.5 and 4.1 times of that on the raw biochar, which induced enhanced adsorption of O3 and its subsequent decomposition into •OH. Electron transfer via redox pairs on MnOx/biochar and FeOx/biochar was observed by cyclic voltammetry scans, which also functioned in the improved catalytic capacity. Degradation pathways of ATZ in MnOx/biochar and FeOx/biochar ozonation systems were proposed, with 34.6% and 44.8% of dechlorination effect accomplished within 30 min of reaction, which was improved by 4.1 and 5.3 times compared to pure ozonation. After 12-hour treatment, acute toxicity of ATZ oxidation products was reduced from 38.3% of pure ozonation system to 14.5% and 6.3% of activated ozonation systems with MnOx/biochar and FeOx/biochar, respectively. Mn-loaded biochar and Fe-loaded biochar have great potential for heterogeneous catalytic ozonation of polluted water. Display omitted