In this work, the porosity, graphitization and iron doping of biochar were realized simultaneously by the pyrolysis of biomass and potassium ferrate (KFeO), then the iron-doped graphitized biochar was reduced to synthesize nanoscale zero-valent iron loaded porous graphitized biochar (nZVI/PGBC). 17β-estradiol (E2) is an environmental endocrine disruptor that can cause great harm to the environment in small doses. Experiments illustrated that nZVI/PGBC (100 mg/L) could completely remove E2 (3 mg/L) within 45 min by activating sodium persulfate (PS, 400 mg/L). The E2 removal efficiency of nZVI/PGBC was obviously superior to that of pristine biochar (BC), iron-doped graphitized biochar (Fe/GBC), nanoscale zero-valent iron (nZVI) and porous graphitized biochar (PGBC). The removal efficiency could be affected by reaction conditions, including reaction temperature, acidity, dosage of catalyst and oxidant and water matrix. Quenching experiments and electron spin resonance (ESR) demonstrated that SO and HO were both responsible for E2 degradation. This study indicated that Fe and Fe were the main catalytic active substances, while the catalytic ability of PGBC was not obvious. The reaction mechanism was proposed, that is, PS was activated by electrons provided by the redox reaction between Fe and Fe, and PGBC acted as the carrier of nZVI, the adsorbent of E2 and the mediator of electron-transfer. This study demonstrates that nZVI/PGBC can be used as an effective activator for PS to remove organic pollutants in water.