High cesium (Cs)-bearing sodium borosilicate glasses incorporated with varying concentrations of TiO2 up to 10 mol% at the expense of B2O3 were prepared by the conventional melt quenching method. Physicochemical properties of the glasses studied include Cs volatilization losses, leaching, and glass transition temperatures. Structural aspects of the glasses were investigated using Fourier transform infrared, 11B MAS NMR, and UV-visible optical absorption techniques. From the detailed investigations on these glasses, optimum concentration of TiO2 for minimum volatilization losses of Cs has been established. Structural studies revealed the role of TiO2 in the Cs volatilization as well as leaching characteristics of the glass. Based on our studies, it can be inferred that the glass sample with 5 mol% TiO2 content gives the optimum formulation with regard to the leaching and Cs volatilization losses. Results of the study are useful in the development of high Cs-bearing glasses for their use as a gamma source for radiation technology application.