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Several physical, optical absorption and photoluminescence properties of Eu3+-doped ZnF2–PbO–TeO2 glasses have been studied. From the measured intensities of various absorption bands of these glasses the Judd–Ofelt parameters Ω2, Ω4 and Ω6 have been computed. The Judd–Ofelt theory has been applied to characterize the photoluminescence spectra of these glasses. From this theory, various radiative properties, such as transition probability, A, branching ratio, βr, and emission cross-section, σEP, for various emission levels of these glasses, have been determined and reported.