The high phonon energy oxide of B₂O₃ is introduced into the Er³⁺/ Ce³⁺co-doped tellurite-niobium glasses with composition of TeO₂-Nb₂O₅-ZnO-Na₂O. The absorption spectra, 1.53 μm band fluorescence spectra, fluorescence lifetime and Raman spectra of Er³⁺in glass samples are measured together with the calculations of Judd-Ofelt spectroscopic parameter, stimulated emission and absorption cross-sections, which evaluate the effect of B₂O₃ on the 1.53 μm band spectroscopic properties of Er³⁺. It is shown that the introduction of an appropriate amount of B₂O₃ can further improve the 1.53 μm band fluorescence intensity through an enhanced phonon-assisted energy transfer (ET) between Er³⁺/ Ce³⁺ions. The results indicate that the prepared Er³⁺/ Ce³⁺co-doped tellurite-niobium glass with an appropriate amount of B₂O₃ is a potential gain medium for the 1.53 μm bandbroad erbium-doped fiber amplifier (EDFA).