Eu 3+ doped boro-tellurite glasses with the chemical composition (69 − x)B 2O 3– xTeO 2–15Mg 2O–15K 2O–1Eu 2O 3 (where x = 0, 10, 20, 30 and 40 wt%) have been synthesized and its thermal, structural and spectroscopic behavior were studied and reported. The thermal behavior of the Eu 3+ doped boro-tellurite glasses were explored through DTA thermograms. The presence of varying tellurium dioxide results in structural and spectroscopic changes around Eu 3+ ions and are explored through XRD, FTIR, UV–vis, Luminescence and lifetime measurements. The XRD pattern confirms the amorphous nature and the FTIR spectra reveal the formation of the local structural units BO 3 and BO 4 in the prepared glasses. The bonding parameters (̄ β and δ) have been calculated based on the observed band positions of the absorption spectra. The Judd–Ofelt (JO) parameters were determined from the absorption and luminescence spectra and the results are presented. The variation in the JO intensity parameters Ω λ ( λ = 2, 4 and 6) and the hypersensitive band positions with the change in chemical composition have been discussed in detail. The JO parameters have been used to derive important radiative properties like transition probabilities ( A), branching ratios ( β R) and peak stimulated emission cross section ( σE/ P) for the 5D 0 → 7F J ( J = 1, 2, 3 and 4) transitions of the Eu 3+ ions. The varying optical properties of the prepared glasses with the change in tellurium dioxide have been studied and compared with similar results.