Bi-doped BaO-B2O3 glasses are prepared by the melting method. Visible and infrared luminescence spectra, fluorescence decay curve and Raman scattering spectra are measured. NIR emissions, not only one broadband emission peak but also several emission peaks, appear in Bi-doped BaO-B2O3 glass under 808 nm LD pumping. The effect of the network structure of BaO-B2O3 glass on the NIR emission is discussed, and the mechanism for the emission is investigated preliminarily.