Peroxymonosulfate-based advanced oxidation process (PMS-AOP) has shown great potential in sewage purification, and catalyst development capable of efficient PMS activation is a key while challenging element. Herein we reported a facile electro-explosive route to synthesize the oxygen vacancy (Vo)-enriched Mo/MoO 2 without using chemical reagents. The detailed studies suggested that the synergy of Mo active site and Vo in the catalyst significantly boosted the activation kinetics of PMS. Evidently, the Mo site of different oxidation states contributed to chemical activation of PMS, while the Vo favored the activation of PMS and the generation of non-radical 1 O 2 species. As a result, the Mo/MoO 2 -10 h/PMS system delivered a complete removal of acid orange 7 (AO7) within 4 min, significantly exceeding the activity of Mo/PMS (16%), MoO 2 -H/PMS (25%) and most of other PMS-based systems. Moreover, the current system showed high potential for removal of different pollutants including antibiotics and organic dyes. Radical quenching experiments and electron paramagnetic resonance (EPR) studies revealed that the 1 O 2 species was significant for AO7 decomposition. This work provided a novel strategy to a batch-scale synthesis of high-performance PMS activator for water remediation in practice.