AbstractThe dispersive, reusable catalyst and convenient separation is still a key factor for water treatment. Herein, the Fe0/Fe3O4/Fe3C@ hydrophilic carbon composite catalyst was obtained through thermal reduction, in which Fe0 is generated by in‐situ carbothermal reduction of the rationally designed gel precursor. The FTIR, SEM‐EDX and the XPS analysis revealed that the major hydrophilic functional groups and elements were well‐dispersed on the entire surface of the catalyst. Through batch control experiments, it is shown that the synthetic catalyst can significantly accelerate the catalysis of Methylene blue under the radiation of 30 W LED lamp. The Electron Spin Resonance test further confirms that catalyst could be successfully trap ⋅OH radicals. With the increase of radiation time, such energy changes affect the coupling effect of spin‐orbital motion is stronger leading to changes in the g‐anisotropy. Organic pollution can be degraded by the porous catalyst in a photo‐Fenton reaction with the degradation efficiency rate approaching nearly 100 % when the concentration of H2O2 is 7 mm. The reusability was demonstrated by five consecutive reaction cycles at continuously good performance. This work provides a highly promising and facile strategy for many wastewater treatments, especially in the field of photo‐Fenton like reaction to environmental modification.