There emerges an urgent stipulation towards the enhanced toluene catalytic combustion nanocatalysts for whittling down the footprint of toluene, a notorious air pollutant. Unfortunately, Few materials which are currently made accessible both present the high catalytic performance lower than 250 °C and keep durable at elevated temperatures. Herein, we demonstrate an expeditious salt hydrolysis-driven redox-precipitation protocol wherein H+ donated by the hydrolysis of copper salt was used to initiate the regioselective reduction of KMnO4 by H2O2 under controlled redox kinetics in order to assemble the homogeneous mixed solid solution hollow microsphere Cu-Mn-based structure. Manifold characterization technologies unveil that in this unique nanbomicrosphere the abundant microscaled pores are successfully created across Cu-Mn bulks with fine-modulating the chemical properties. In sharp contrast with the compact counterparts without tailed porosity, the tuned crystallinity, accessed edge sites with the unsaturated coordination, fast redox chemistry, and boosted gaseous diffusion during reactions synergize to result in the signally good toluene oxidation, with the complete elimination activity at 252 °C, T90 at 237 °C, and prominent long-term durability under the stringent reaction atmospheres. Our current study ushers in an alternative and tractable arena to excogitate the porous oxide materials for multifarious catalysis implementations.