A melt quenching technique was used for the preparation of xBaO–(30-x)TeO2–35Bi2O3–33B2O3–2V2O5 (5 ≤ x ≤ 25 mol%) glasses. The structural modifications are studied by X-ray diffraction, DSC, optical, infrared spectroscopy, and Raman as a function of BaO mol%. The progressive incorporation of BaO mol% in the BTBiBV glasses decreases the optical band gap values as the number of free electrons increases with the creation of additional NBOs. The FTIR spectra of the prepared glasses consist of BO3 trigonal and BO4 tetrahedral units while TeO2 changes to TeO3 andTeO4 structural units. The Raman spectra shows that the replacement of BaO with TeO2 decreases the concentration of Te–O–Te linkages within the volume of host glass, which increases the concentration of Ba–O–Te linkages along with BO3 units. Due to this, the overall glass formers connectivity decreases which intern to the creation of NBOs. Moreover, the research highlighted that BTBiBV-5 glasses have exceptional optical properties making them promising materials for photonics, optoelectronics, and optical communication device applications.