Barium sodium borosilicate glasses containing different amounts of uranium oxides were prepared by conventional melt quench method and investigated for their structural aspects by 29Si and 11B 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 15 wt% 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 15 wt% 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 25 wt% uranium oxides, crystalline barium uranium silicate gets phase separated from glass matrix as confirmed by XRD studies.