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Monoclinic Mn₅O₈, spinel Mn₃O₄, and perovskite Mn ₂O₃were prepared by thermal decomposition of MnC₂O₄. The formation of different MnOx species observed by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) measurements showed temperature-dependent phase transformation following the path of MnC₂O ₄$\to$Mn₅O₈$\to$Mn₃O₄$\to$Mn₂O ₃occurring during the heat treatment process. Among these manganese oxides, the MO-1 (Mn₅O₈ ) showed the best light-driven photothermal catalytic performance reaching up to 99% of toluene degradation and 75% of mineralization efficiencies reached within 30 min. Besides, it is found that structural defects decrease with the increase of the calcinated temperature, and the Mn${}^{4+}$/Mn${}^{3+}$active sites and oxygen vacancies play an important role in improving the light-driven photothermal catalytic performance.