The hydrothermal method was used to synthesize α-MnO 2 with nanoflower-like (NF) and nanowire-like (NW) morphologies. Besides, different amounts (5−15 wt %) of silver were loaded into flowerlike α-MnO 2 (Ag(x)-NF) to promote the soot oxidation performance. The resulting catalysts have been characterized by different techniques. Soot oxidation was detected over temperature-programmed experiments. Unequal surface oxygen vacancies in different α-MnO 2 result in different O x n− generating capacities, as shown in the X-ray photoelectron spectroscopy (XPS) test. The NF had the highest ratio of highly reactive superoxide (O 2 − ). In addition, the NF modified by optimal amounts of Ag could speed up the O 2 − generation caused by the largest amount of surface oxygen vacancies. The density functional theory calculation revealed that the oxygen vacancies on α-MnO 2 species could improve the adsorption of reactants and increase the surface energy of the asprepared catalyst, which result in excellent catalytic performance of Ag(10)-NF.