In this paper, an attempt to explore the use of laser induced breakdown spectroscopy (LIBS) technique for determination of uranium in the vitrified simulated high level barium borosilicate waste glass matrix was made with a commercial portable LIBS system. The emission spectrum of the waste glass being very complex, detailed study was done for proper choice of the emission lines. Investigations were carried out to optimize the experimental parameters like laser energy and acquisition delay time for the analysis. Calibration curves were obtained for two emission lines of U in these glasses. Effect of Ar atmosphere was also studied and the signal intensity was found to be ~5 times higher than in air atmosphere The emission lines used for normalization with vast difference in the upper energy level compared to the line of interest were found to give poor precision in air. In the Ar atmosphere, this effect was found to be much less significant and such emission lines can be used as an internal standard to achieve precise calibration curves. LIBS approach will be useful for real time determination of U in such samples, eliminating quantitative dissolution step required in  many other analytical techniques like solution based ICPMS/OES.