The valence states of the Mn ions in Pr 1−x A x MnO 3−δ (A=Ca, Sr) are investigated by Mn-L 3 X-ray absorption near-edge structure (XANES) analysis. The spectral fine structures in the Mn-L 3 XANES analysis show a significant difference between Pr 0.5 Ca 0.5 MnO 3−δ and Pr 0.5 Sr 0.5 MnO 3−δ , a paramagnetic insulator and a ferromagnetic metal, respectively, at room temperature, whereas the spectral structures of Pr 0.7 Ca 0.3 MnO 3−δ and Pr 0.7 Sr 0.3 MnO 3−δ , paramagnetic insulators, are almost identical. These results indicate that the valence states of the Mn ions in these materials are highly correlated with their magnetic and electrical properties. A significant difference was also found between the Mn-L 3 XANES profiles of Pr 1−x Ca x MnO 3−δ and the profiles formed by the linear combination of the Mn-L 3 XANES spectra of PrMnO 3 (Mn 3+ ) and CaMnO 3 (Mn 4+ ). This difference indicates that the Mn ions in these materials do not have a mixed-valence state of 3+ and 4+, but have an intermediate valence state o 3+ and 4+.