<p>In Fenton-like reaction activated by peroxymonosulfate (PMS), compared to SO₄^•− produced <i>via</i> the electron acceptance path, ¹O₂ generated from electron donation path were more attractive. Herein, PMS activation path was altered from SO₄^•− to ¹O₂ through improving Lewis acidity on catalytic sites. During ZIF-67 preparation, vanillin (VAN) was introduced to regulate the chemical environment around the Co^3+/2+ nodes. The coordinated N atoms in 2-methylimidazole were partially substituted by O atoms in VAN, leading to the enhanced Lewis acidity on Co^3+/2+ sites. In this case, Lewis base PMS were likely to donate electrons to electron-deficient Co^3+/2+ sites, and ¹O₂ were generated as the primary radicals. Besides, coordinatively unsaturated metal sites (CUMSs) were produced during the substitution process, since Co^3+/2+ nodes were not fully bridged by VAN ligands. This improved the PMS utilization efficiency and ¹O₂ yield. Previous studies have indicated the metal leaching would be worsened by CUMSs, owing to the lack of ligand protection. To solve this problem, a Co₂SiO₄ shell was coated on VAN-ZIF-<i>x</i> surface. VAN-ZIF-<i>x</i>@Co₂SiO₄ yolk@shell nanoreactor not only suppressed the metal leaching, but also improved the environmental adaption. This paper gave a novel insight on altering the PMS activation path, together with the CUMSs creation on catalyst surface.</p>