To explore effective way for the complete catalytic degradation of toluene at low temperature, catalysts with diverse activity of adsorbed oxygen (O_ads) and lattice oxygen (O_latt) are synthesized by introducing Sr²⁺ into the birnessite structure. Sr modification highly improved low-temperature catalytic activity and CO₂ selectivity of toluene oxidation under moist condition, especially on the BS-7.5 (Sr:Mn = 0.075) catalyst. A series of physiochemical characterizations and DFT calculations identified abundant O_latt with higher activity in Sr-doped birnessite and higher activity of O_ads in pure birnessite. In situ DRIFTS analysis further confirmed that activation of O_latt introduced by Sr replacement of Mn governed the reaction process towards continuous deep oxidation of toluene. These findings provide a deeper understanding of the mechanism of toluene degradation and strongly pave a way for improving the complete catalytic oxidation performance of VOCs at low temperature over MnO₂ catalysts from the aspect of regulating active oxygen-related properties.