The reduction behavior of Fe and Mn ions and the changes in metal–oxygen polyhedra in cubic perovskite-type SrFe1–xMnxO3−δ(SFM) induced by heating under N2flow were investigated with X-ray diffraction, X-ray absorption fine structure spectroscopy, and Mössbauer spectroscopy. Both the Mn and Fe valences decreased, and metal–oxygen polyhedra in the as-prepared SFM samples with 0.1 ≤ x≤ 0.4 varied with N2heating, showing agreement with reported thermodynamic predictions. The valence state and local atomic structure of Mn ions with sixfold coordination in MnO6octahedra in SrFe0.5Mn0.5O3−δand SrFe0.4Mn0.6O3−δwere retained upon N2heating. The results indicate that the reduction of Fe ions and the flexibility of Fe–O polyhedra in the perovskite-type structure can accommodate the distortion due to oxygen desorption, suppressing the reduction of Mn4+for the SFM samples with x= 0.5 and 0.6. Understanding the different reduction behaviors of Mn ions is essential for the design of new oxygen storage materials.