Herein, flower-like BiOI micro-spherulites were successfully prepared via a solvothermal method, and it exhibited a remarkably Fenton-like catalytic efficacy in the degradation of BPA under dark condition without additional energy input. BiOI can function as an electron-poor center, facilitating the activation of H₂O₂ into •O₂⁻, while simultaneously serving as an electron-rich center to reduce dissolved O₂ to •O₂⁻. This electron-rich and electron-poor centers of BiOI synergistically enhance the •O₂⁻ generation for highly Fenton-like catalytic performance. Moreover, the removal performance of BPA demonstrated a significant pH dependency, and the presence of low concentrations of halide ions and humic acid did not exhibit noticeable inhibitory effect on the degradation of BPA. Additionally, several intermediates have been identified to propose a comprehensive degradation mechanism for BPA. This study presents a novel BiOI Fenton-like catalytic system for the purification of recalcitrant organic pollutants in wastewater.