We report on the visible and near-infrared luminescence properties of Bi-doped sodium borosilicate glasses. The emission intensity at 420 nm due to the transition of Bi(3+) decreases with increasing B(2)O(3) concentration. Boron anomaly features were observed in both the visible emission at 618 nm due to the transition of Bi(2+) and the near-infrared emission at 1340 nm due to the transition of Bi(+). We have proposed a mechanism that suggests Bi(+) to be responsible for the near-infrared luminescence, and [BO(4)] units play an important role for stabilizing Bi ions with low valence state in glasses. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3586039] All rights reserved.