Nanoscale zerovalent iron (nZVI) particles have received much attention in environmental science and technology due to their unique electronic and chemical properties. However, the aggregation and oxidation of nZVI brings much difficulty in practical application of environmental remediation. In this study, we reported a composite nano-Fe(0)/mesoporous carbon by a chelation-assisted coassembly and carbothermal reduction strategy. Nano-Fe(0) particles with surface iron oxide (FeO·FeO) were wrapped with graphitic layers which were uniformly dispersed in mesoporous carbon frameworks. The unique structure made the nano-Fe(0) particles stable in air for more than 20 days. It was used as a peroxydisulfate (PDS) activator for the oxidation treatment of 2,4,6-trichlorophenol (TCP). The TOF value of MCFe for TCP degradation is nearly 3 times higher than those of FeSO and FeO·FeO and nearly 2 times than that of commercial nZVI. The reactive oxygen species (ROS) including •SO, HO•, and •O, O are efficiently generated by PDS activation with MCFe. The PDS activation process by nano-Fe(0) particles was intrinsically induced by the ferrous ions (Fe(II)) continuously generated at the solid/aqueous interface. Namely, the nano-Fe(0) particles were highly efficiently utilized in sulfate radical-based advanced oxidation processes (SR-AOP). The porous structure also assists the absorption and transfer of TCP during the degradation process.