The effect of V2O5 addition on sealing properties of glasses with nominal composition (29-x)SiO2–23SrO–32BaO–4Al2O3–10B2O3–2P2O5-xV2O5 (where x = 2; 4; 6 mol.%) is reported. The glass transition temperature (Tg) decreases, and flow temperature increases with an increase in V2O5 content. 29Si and 31P MAS-NMR indicate that silicates are present mainly as Q2 groups, while phosphates are present as Q0 groups. 27Al MAS-NMR data shows that Al is 4-coordinated with oxygens, and11B NMR spectra show the presence of both BO3 and BO4 units. Composite materials were prepared by mixing glasses and vanadium di-boride VB2 (15 vol%). Sealing with Crofer-22 alloy was carried out with composite and revealed good bonding and tight interfaces.