Bulk glasses of the series (100−x)[0.4Na2O-0.2Nb2O5-0.4P2O5]-xB2O3 with x = 0–48 mol% B2O3 were prepared by slow cooling in air. Their glass transition temperature increases within the range of 0–16 mol% B2O3, but further additions of B2O3 result in its decrease. Their structure was investigated by Raman, 11B, and 31P MAS NMR spectroscopy. The relative number of BO4 units decreases with increasing B2O3 content, while the number of BO3 units increases up to 59 % at x = 48. The upfield shift of a broad resonance peak in the 31P MAS NMR spectra is ascribed to an increasing connectedness of the structural network with increasing B2O3 content. Strong Raman band at 916–929 cm−1 shows on the presence of NbO6 octahedra in the structural network of these glasses. With the B2O3 addition, a decrease in DC conductivity is observed, which is attributed to the decrease in the concentration of Na+ ions.