A novel catalyst of sulfidated iron-nickel supported on biochar (S-FeNi@BC) was synthesized to activate persulfate (PS) for the removal of trichloroethylene (TCE). A number of techniques including XRD, SEM, TEM, FTIR, BET and EDS were employed to characterize S-FeNi@BC. The influence of sulfur to iron ratio (S/F) on TCE removal was investigated by batch experiments and a higher TCE removal (98.4%) was achieved at 0.22/1 ratio of S/F in the PS/S-FeNi@BC oxidation system. A dominant role in iron species conversion was noticed by the addition of sulfur in FeNi@BC system. Significant enhancement in recycling of the dissolved and surface Fe(II) was confirmed which contributed to the generation of free and surface-bound active radical species (OH, O2−, 1O2, SO4−). Further, the presence and contribution of these radicals were validated by the electron paramagnetic resonance (EPR) and quenching study. In addition, XPS results demonstrated the dominant role of S(-II) with the increase of Fe(II) from 36.3% to 58.6% and decrease of Fe(III) from 52.1% to 39.8% in the PS/S-FeNi@BC system. In crux, the influence of initial pH, catalyst dosage, oxidant dosage, and inorganic ions (HCO3−, Cl−, NO3− and SO42−) on TCE removal was also investigated. The findings obtained from this study suggest that S-FeNi@BC is an appropriate catalyst to activate PS for TCE contaminated groundwater remediation.