In this study, the oil sand was treated with an integrated process of pyrolysis and ball milling, and the obtained ball-milled carbon sand (BMCS) was utilized as peroxymonosulfate (PMS) activator to treat wastewater containing aniline (AN). Quenching experiments and electron paramagnetic resonance (EPR) confirmed the existence of sulfate radical (SO4∙‐), hydroxyl radical (·OH) and singlet oxygen (O12) in the BMCS/PMS system. A probe-based kinetic model was constructed to describe the degradation process of pollutants in the BMCS/PMS system, quantified the exposure of each reactive oxygen species and their contributions to AN degradation. BMCS activated PMS to quickly produce SO4∙‐ and gradually generate ·OH. The O12 exposure showed a rapid increasing trend and the largest total exposure, while its contribution to AN degradation was small. Ball milling time and BMCS dosage demonstrated significant effect on the exposure of ·OH and O12. The main active sites for BMCS to activate PMS were iron oxides, defective carbon and oxygen-containing functional groups. This study provides a green and low-cost process for value-added transformation of pyrolytic residue of oil sand (PROS), so as to promote PROS treatment mode from harmless disposal to resource utilization.