Different glasses in the system, xV₂O₅-(45–x)B₂O₃–24.5Na₂O–24.5CaO–6P₂O₅, (x = 0, 3, 6, 9, 12, 15, 18, 20 and 25 Wt%) were prepared through melt quenching method. X-ray diffraction (XRD) patterns have revealed that the amorphous structure is the dominant type. There is no tendency for crystallization even with higher vanadium content. Crystallization occurred utilizing treating the glasses thermally. FTIR spectral absorption data showed the presence of both BO₃ and BO₄ structural groups in combination with the presence of VO₄ and VO₅ structural building units. The deconvolution analysis technique (DAT) was adopted to retrace the conversion progressions of the coordinated boron. At low V₂O₅ content (up to 10 wt%), it entered as a glass modifier as well as both Na₂O and CaO. The high content of the glass modifier (Na₂O + CaO + V₂O₅) could destroy some of the well-formed BO₄ units which are transformed into asymmetric BO₃. The back conversion of BO₄ to asymmetric or loose BO₃ can simply reduce the fraction of tetrahedral units (N₄). When V₂O₅ entered as a glass former (> 10 wt%), the N₄ fraction increased. The change in the measured densities and estimated molar volumes may assigned to the formation of BO₄ units resulting from increasing vanadium oxide content.