MnO2-based materials have been extensively investigated for the elimination of aromatic volatile organic compounds (VOCs). Nevertheless, their practical performance is limited by sluggish activation-consumption-replenishment kinetics of key oxygen species. Here, we have successfully engineered Cu-O-Mn and Ce-O-Mn asymmetric centers within MnO2. Their successful construction not only gives rise to Cu-Ov-Mn and Ce-Ov-Mn defect sites but also refines the electron transfer efficiency between metal and oxygen species in CeCu-MnO2. The Cu-Ov-Mn or Ce-Ov-Mn defect sites promote the adsorption of gaseous oxygen onto the CeCu-MnO2 surface while simultaneously facilitating the migration of lattice oxygen, thereby substantially accelerating the activation-consumption-replenishment cycle of reactive oxygen species. Consequently, CeCu-MnO2 exhibits catalytic activity markedly superior to that of Ce-MnO2 and Cu-MnO2. Its T90 is lowered by 25 °C and 33 °C relative to Cu-MnO2 and Ce-MnO2, respectively, and its low-temperature reaction rate is nearly twice as high as that of the latter two. Moreover, CeCu-MnO2 demonstrates excellent catalytic stability and water resistance, confirming its immense potential for industrial application.