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Oxyfluoride lead borate glasses singly doped with Nd3+ and Er3+ ions have been studied before and after thermal treatment. The orthorhombic PbF2 crystallites are formed during thermal treatment, which was evidenced by X-ray diffraction analysis. Near-infrared luminescence spectra at 1.06 μm and 1.53 μm have been registered for samples before and after annealing, which correspond to the main 4F3/2–4I11/2 and 4I13/2–4I15/2 laser transitions of Nd3+ and Er3+ ions, respectively. Luminescence decays from 4F3/2 state of Nd3+ and 4I13/2 state of Er3+ have been analyzed in detail. Contrary to Nd-doped samples, the luminescence lines obtained for Er-doped transparent oxyfluoride glass-ceramics are more intense and narrowed, whereas the luminescence decays from 4I13/2 state of Er3+ are slightly longer in comparison to precursor glasses.