Glasses of the composition (30-x)PbO–5Bi 2 O 3 –65SiO 2 : xNiO (with x ranging from 0 to 1.0mol%) were synthesized. A variety of spectroscopic studies, viz., IR, Raman optical absorption and luminescence properties of these glasses have been carried out as a function of NiO concentration. The analysis of results of all these studies has indicated that the nickel ions occupy both octahedral and tetrahedral positions. However, with the increase of NiO concentration the octahedral occupancy of Ni 2+ ions prevailed over the tetrahedral ions. The luminescence spectra of these glasses have exhibited a broad NIR emission band in region 1100–1500nm. This band is identified as being due to 3 T 2 (3F)→ 3 A 2 (3F) octahedral transition of Ni 2+ ions. The luminescence efficiency and cross section have been found to be the highest for the glass containing the highest concentration of NiO. The reasons for such high luminescence efficiency have been discussed in the light of structural variations taking place in the host glass network.