Sulfate radical advanced technologies (SR-AOPs) has been increasingly applied for chemical oxidation of toxic wastewater treatment, while the sluggish kinetics of Fe(III)/Fe(II) cycling remains a serious problem in its application. In this study, a novel co-catalyst of humic acid-Fe incorporated biochar (HA-Fe@BC) was successfully synthesized that can greatly accelerate the Fe(II) regeneration. More than 95 % organic pollutants could be degraded in HA-Fe@BC/peroxydisulfate (PDS) system, especially for the model pollutant Rhodamine B (an almost 8.0-fold kinetic increase). More excitingly, the superior catalytic activity of HA-Fe@BC for PDS activation may be attributed to the ample surface C-OH and C=O groups, accelerated electron transfer and formed surface HA-Fe@BC-PDS* complex with efficient oxidation activity. Radical capture, quenching experiments and electrochemical analysis confirmed that the HA-Fe@BC/PDS was caused by radicals (SO4 center dot-+ O-2(center dot-)+center dot OH = 68.13 %) and non-radical (surface-mediated electron transfer and O-1(2) = 26.33 %) pathways. Besides, it also exhibited antiinterference performance against anions and organic matter (eg. Cl-, Br-, NO3-, and PO43-). Furthermore, the degradation pathways were proposed by LC-MS assisted with density functional theory (DFT) calculations, and the mechanism was proposed comprehensively. This work demonstrates the PDS activation by HA-Fe@BC through free radical and non-free radical pathways, which provides insight into application of biochar-based materials for wastewater treatment.