The residual of oxidant chemicals in advanced oxidation processes (AOPs) resulted in both economic cost and secondary pollution. Herein, we report a direct oxidation of phenolic pollutants induced by Ca-Mn-O perovskites without using an oxidant. Governed by one-electron transfer process (ETP) from the phenolics to the Ca-Mn-O perovskites, this direct oxidation proceeds in fast reaction kinetics with activation energy of 51.4 kJ/mol, which was comparable with those AOPs-based catalytic systems. Additionally, mineralization and polymerization reactions occurred on the Ca-Mn-O surface and ensured the complete removal of phenolics. The high spin state Mn(III) within Ca-Mn-O structure was the dominant active site for this ETP. The elongated axial Mn(III)–O bonds within the [MnO₆] octahedron facilitated the acceptance of the electrons from the phenolics and thus promoted the initiation of the direct oxidation process. Mn(III) in the high spin state can also activate dissolved O₂ to produce singlet oxygen (¹O₂) for a fast removal of phenolics. The mixed Mn(III)/Mn(IV) within Ca-Mn-O accelerated the ETP by enhancing the electrical conductivity. This efficient Ca-Mn-O-induced ETP for removal of organic contaminants casts off the dependence on external chemical and energy inputs and provides a sustainable approach for transforming the toxic organic pollutants into value-added polymers.