Efficient decomposition of organic pollutants in complex soil environments through non -radical pathways is vital but challenging. Herein, biochar supported nZVI (nZVI@BC800) fabricated by carbothermal reduction method was prepared for persulfate activation, exhibiting ultrafast degradation efficiency of benzo[a]pyrene of 71.80 % within 5 min with excellent adaptability to wide pH range of 3.0-9.0 and high anti -interference capacity to coexisting substances in soil. In nZVI@BC800/persulfate system, non -radical pathways including singlet oxygen (O-1(2)) and electron transfer made dominant contributions to benzo[a]pyrene degradation. O-1(2) could be produced not only by the reaction between C = O on BC800 and persulfate, but also via the transformation of O-2(center dot-) and center dot OH. On the other hand, biochar as an electron shuttle could accelerate electron transfer from benzo[a]pyrene to persulfate adsorbed on the catalyst. Additionally, possible degradation pathways of benzo[a]pyrene in nZVI@BC800/persulfate system were inferred through GC-MS and DFT calculations. Furthermore, the system could modulate the soil microbial community to further improve plant stress resistance. Therefore, this study provided a promising strategy via developing carbon -supported iron catalyst for carrying out persulfate-based non -radical pathways to remediate organic -polluted soil.