The spectroscopic properties and thermal stability of Er2O3 doped Bi2O3–B2O3–Na2O glasses are investigated experimentally. A close correlation is observed between the B2O3 content and the spectroscopic properties such as Judd–Ofelt intensity parameters Ωt (t=2,4,6), emission spectra, and lifetime of I13/24 level of Er3+. The value of Ω6 increases with an increase of B2O3 content, which is attributed to the decrease of the covalency of Er–O bond in terms of the glass microstructure and electronegativity theory. The emission spectra of I13/24→4I15/2 transition broadens as a consequence of the enhancement of the inhomogeneous distribution of Er3+ sites when increasing B2O3 content. The lifetime of I13/24 level of Er3+ in bismuth-based glass, compared with those in other glasses, is relative low due to the high-phonon energy of the B–O bond, the large refractive index of the host, and the existence of OH− in the glass. In addition, the glass stability is improved in which the substitution of B2O3 for Bi2O3 strengthens the network structure. The suitability of bismuth-based glass as a host for Er3+ doped for a broadband amplifier and its advantages over other glass hosts are also discussed.