It is of fundamental significance to rationally design the potent toluene-oxidation nanocatalysts for alleviating the release of toluene, one hazardous volatile organic compound, from industrial processes, oil products and fitments materials. The manganese oxide has been developed as the extremely robust combustion materials for a wide spectra of application involving methane combustion, CO oxidation and so forth, but still has been haunted with the poor behavior for toluene combustion. Herein, we successfully demonstrate a one-step scenario wherein the well-structured LaMnO3 perovskites are in situ assembled over delta-MnO2 for the first time. Various characterizations unravel that the LaMnO3 perovskites interact with delta-MnO2 to result in good catalytic toluene combustion behavior at the Mn/La ratio of 15. Boosted active phase-carrier interplays, improved redox abilities, and tuned Mn4+/Mn3+ couples ultimately result in the decent toluene combustion property with the full toluene oxidation at 275 degrees C and T-90 at 258 degrees C. The nanostructured scalable MnO2-based materials are promising catalyts that can be extended to degrade alkane, alcohols, aldehydes and benzene series.