Core–shell ZIFs wrapped CuO hybrid materials (CuO@ZIF-67(Co)) were designed, synthesized, characterized, and employed as peroxymonosulfate (PMS) activators to degrade methylene blue (MB). It demonstrated outstanding catalytic activity on account of the unique structure and the synergistic effect between CuO cores and ZIF-67(Co) shells, resulting in complete degradation of MB (10 mg/L) in 1 min. Reactive oxygen species (ROSs) research showed that both SO4 − and OH were responsible for the removal of MB. The synergistic activation mechanisms in the CuO@ZIF-67(Co)/PMS system were investigated, which mainly involved the effective electron transfer of CuO and ZIF-67(Co) for accelerating the cycle of CuII/ CuI and CoIII/ CoII. This study broadens the application of MOF-derived materials for wastewater treatment.