To study the oxygen vacancies evolvement on the single component and the bi-components manganese oxides, two manganese oxide precursors (Mn5O8 and MnO2-Mn3O4) with similar Mn/O ratio were prepared and were treated by air, N-2, and Ar, respectively. The morphology, composition and structure of the prepared samples were characterized by FE-SEM, XRD, XPS, EPR, STEM, STEM-EDS and N-2 adsorption-desorption. The valence state evolvement indicates that the Mn5O8 and MnO2-Mn3O4 are all transformed into MnO, Mn3O4 and MnO1.88 with different proportions. The results showed that the oxygen vacancies contents of the as-prepared samples are not only related to the treating atmosphere but also heavily dependent on the atom ratios of Mn and O of the precursors. Compared with the heat treated MnO2-Mn3O4, the heat treated Mn5O8 presented higher oxygen vacancies content and more Mn atoms dislocating structure, suggesting that the single component Mn5O8 is helpful to promoting the formation of defects. These findings reveal that the single component Mn5O8 is helpful to the formation of oxygen vacancies, ultimately resulting in an enhanced catalytic combustion performance of toluene. The oxygen vacancies evolvement of the single component and the bi-components manganese oxides were explored. Compared with the nanorods-Ar, the spindles-Ar shows more oxygen vacancies and dislocating Mn atoms, and enhanced catalytic combustion performance of toluene. [GRAPHICS] .