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Photocatalytic ozonation is an attractive advanced oxidation process for wastewater treatment, but highly active catalysts with strong response to visible light are urgently needed to push forward its practical application. In this study, a hierarchical biomimetic monoclinic bismuth vanadate (BiVO 4 ) with leaves morphology was synthesized by a hydrothermal method, and employed as catalyst for oxalic acid and penicillin degradation in photocatalytic ozonation. The results show that the organics degradation was more efficient using leaves shaped BiVO 4 as catalyst than the bulk shaped one in photocatalytic ozonation and the synergy index is ranged from 2.8 to 3.3, indicating a superior positive synergistic effect between photocatalysis and ozonation. The higher activity of the leaves shaped BiVO 4 was probably attributed to the distinctive biomimetic morphology and preferable band structure with more negative CB potential. Mechanism studies suggested that the main reactive species were h + and OH for the degradation of persistent oxalic acid in photocatalytic ozonation. In addition, the effect of ozone concentration and inorganic ions and reusability of the material were also intensively investigated., (Copyright © 2019 Elsevier Ltd. All rights reserved.)