Understanding the role of V₂O₅ within borosilicate glass matrices is important for the development of novel matrices toward immobilization of sulfate containing high-level nuclear wastes. Present investigation shows, within sodium barium borosilicate glass matrix V₂O₅ can be homogeneously added up to 5 mol% and beyond which it separates out into three phases, for example, (i) silica (ii) Barium (Ba)–Vanadium (V) oxide, and (iii) glass matrix. ²⁹Si MAS NMR (Nuclear Magnetic Resonance) studies of the samples show that below 5 mol% V₂O₅ addition, silicate network is dominantly constituted of Q²and Q³ structural units, whereas above this, the network gets more polymerized through formation of Q³ and Q⁴ units. In case of borate network, ¹¹B MAS NMR investigations revealed that the concentration of BO₄ [(0B, 4Si)] unit increases gradually up to 5 mol% and then it decreases at the cost of BO₄ [(1B, 3Si)], BO₃ (symmetric) and BO₃ (asymmetric) units. Micro-Raman analyses of the samples showed that with additions of V₂O₅ in diluted concentrations, amorphous silicate network remained unaltered, whereas some amplification in signals corresponding to ring-type metaborate and VO₅ units exists. It is therefore apparent from both MAS-NMR and micro-Raman studies that with V₂O₅ additions within the solubility limit (≤5 mol%), borate network gets depolymerized leading to decrease in hardness from an average value of 5.0–4.2 GPa.