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Energy transfer processes from Cr3+ to Nd3+ and NIR luminescence of Nd3+ ions at 1.06 μm in Cr–Nd co-doped lead borate glasses have been investigated. The spectroscopic investigation indicates that Cr3+ ions are located at strong-field and weak-field sites. Replacing PbO by PbF2 in lead borate glasses slightly influences the energy transfer processes between Cr3+ and Nd3+ and NIR luminescence of Nd3+ ions. The energy transfer process occurs in both oxide and oxyfluoride glass systems, which may be due to the thermally induced population of the 4T2 excited state of Cr3+ ions and the participation of lattice phonons.