In this work we investigate the effect of replacing Na 2 O by TiO 2 on the structural and spectroscopic characteristics of the Nd 2 O 3 -doped 60B 2 O 3 –(20−x)Na 2 O–10PbO–10Al 2 O 3 :xTiO 2 :yNd 2 O 3 borate glass matrix. Measurements of X-ray patterns, glass temperatures (Tg), vibrational (Raman and infrared (IR)) and optical (absorption and emission) spectra were carried out. The trend of Tg, the Judd–Ofelt parameters and Nephelauxetic ratio as the TiO 2 and Nd 2 O 3 concentration increases was interpreted quantitatively and qualitatively in terms of the network bonds and coordination numbers. Measurements of Tg across the Nd-doped glass series for different levels of Ti suggests changes in the rigidity of the matrix due to change of coordination of boron oxide resulting from the BO 4 –BO 3 back conversion effect. The changes observed in the Raman and IR spectra are related to the BO 3 →BO 4 conversion effect. The variation of the Judd–Ofelt parameters Ω(2) and Ω(6) indicates that the average rare earth-ligand radius decreases establishing an electronic density distribution when Nd 3+ concentration increases. This effect is interpreted in terms of Judd–Ofelt parameters and by the bonding parameter b1/2 due to Nephelauxetic effect.