Barium sodium borosilicate glasses containing different amounts of uranium oxides were prepared by conventional melt quench method and investigated for their structural aspects by Si-29 and B-11 MAS NMR technique combined with steady-state luminescence and lifetime measurements. Based on MAS NMR studies, it is confirmed that uranium ions act as network modifier up to 15wt% and beyond which a separate uranium containing phase is formed. From the luminescence studies, it is inferred that uranyl species is in a highly distorted environment. For more than 15wt% uranium oxide incorporation, weaker U-O-U linkages are formed at the expense stronger U-O-Si/B linkages, as suggested by the excited state lifetime value of the uranyl species as well as red shift in emission peak maximum. For glass samples containing more than 25wt% uranium oxides, crystalline barium uranium silicate gets phase separated from glass matrix as confirmed by XRD studies.