Eu‐doped oxyfluoride aluminosilicate glasses were prepared by melt‐quenching method. The glass samples were characterized by photoluminescence (PL) spectroscopy and electron paramagnetic resonance techniques. In the glass samples, the reduction of Eu3+ to Eu2+ ions occurred in the air condition. The PL spectra showed that the intensity of 4f65d→4f7 transition of Eu2+ ions increased and the corresponding peak wavelength decreased with increasing fluorine anion concentration. Meanwhile, the relative emission intensity ratio of Eu2+ to Eu3+ also depended on the content of fluorine anions. A possible reduction mechanism was discussed.
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