The development of new strategies to improve the removal of organic pollutants with permanganate (KMnO₄) is a hot topic in water treatment. While Mn oxides have been extensively used in Advanced Oxidation Processes through an electron transfer mechanism, the field of KMnO₄ activation remains relatively unexplored. Interestingly, this study has discovered that Mn oxides with high oxidation states including γ-MnOOH, α-Mn₂O₃ and α-MnO₂, exhibited excellent performance to degrade phenols and antibiotics in the presence of KMnO₄. The MnO₄^- species initially formed stable complexes with the surface Mn(III/IV) species and showed an increased oxidation potential and electron transfer reactivity, caused by the electron-withdrawing capacity of the Mn species acting as Lewis acids. Conversely, for MnO and γ-Mn₃O₄ with Mn(II) species, they reacted with KMnO₄ to produce cMnO₂ with very low activity for phenol degradation. The direct electron transfer mechanism in α-MnO₂/KMnO₄ system was further confirmed through the inhibiting effect of acetonitrile and the galvanic oxidation process. Moreover, the adaptability and reusability of α-MnO₂ in complicated waters indicated its potential for application in water treatment. Overall, the findings shed light on the development of Mn-based catalysts for organic pollutants degradation via KMnO₄ activation and understanding of the surface-promoted mechanism.