In this present work we have studied the physical, structural, thermal, and optical properties of a new set of alkali zinc boro tellurite glasses doped europium trioxide prepared using the melt-quenching method. X-ray diffraction technique (XRD) and SEM were used to determine the non-crystalline property and microstructure property of the prepared samples. By using MAS-NMR spectroscopy and FTIR spectroscopy, the structural changes in the glasses were revealed. The physical properties were described by considering the densities of glass samples and hence molar volume, polaron radius, and oxygen packing density were measured. Thermal stability of glasses was perceived by performing DSC analysis and values ranges from 145 to 190 °C. Using UV–visible absorption spectra, it was possible to calculate the optical properties. The highest refractive index is found as 2.275 for glass AZBTE0 and the lowest is 2.241 for AZBTE5 glass. The ionic behaviour of the glasses was determined by electronegativity and values lie in the range of 1.51 to 1.688. The outcomes of the physical, thermal, and optical characteristics of glasses are intended for potential uses in optical switching and Europium doped fibre amplifier applications.