X-ray absorption spectroscopy (XAS) is performed to study changes in the electronic structures of colossal magnetoresistance (CMR) and charged ordered (CO) La 1−x Ca x MnO 3 manganites with respect to temperature. The pre-edge features in O and Mn K-edge XAS spectra, which are highly sensitive to the local distortion of MnO 6 octahedral, exhibit contrasting temperature dependence between CMR and CO samples. The seemingly counter-intuitive XAS temperature dependence can be reconciled in the context of polarons. These results help identify the most relevant orbital states associated with polarons and highlight the crucial role played by polarons in understanding the electronic structures of manganites.

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