Barium–sodium borosilicate glasses containing upto 6 wt% fluoride ions were prepared by conventional melt quench method and characterized by 19 F, 29 Si and 11 B nuclear magnetic resonance (NMR) techniques. 19 F NMR studies have confirmed the presence of mainly linkages like F–Si(n) or F–B(n) along with F–Ba( n ). Their relative concentrations are unaffected by F − content in the glass. Incorporation of fluoride ions in the glass is associated with significant reduction in the nonbridging oxygen concentration attached to silicon, as revealed by the increase in the concentration of Q 3 structural units of silicon at the expense of Q 2 structural units. 11 B NMR studies have established that the relative concentrations of BO 3 structural units are higher for F − ion containing glasses compared to the one without F − ion incorporation. The observed increase in the relative concentrations of Q 3 structural units of silicon and BO 3 structural units with fluoride ion incorporation in the glass has been attributed to the formation of F–Ba( n ) type of linkages, thereby reducing the concentration of network modifying cations for breaking the Si–O–Si/B–O–B linkages. Formation of such structural units weakens the glass network thereby decreasing the glass transition temperatures.