WO₃oxides with relatively high phonon energy and different concentrations were introduced into the Nd³⁺-doped tellurite- based glasses of TeO₂-ZnO-Na₂O to improve the 1.32 μm band fluorescence emission. The absorption spectra, Raman spectra, 1.32 μm band fluorescence spectra and differential scanning calorimeter (DSC) curves were measured, together with the Judd-Ofelt intensity parameters, stimulated emission and gain parameters were calculated to evaluate the effects of WO₃amount on the glass structure and spectroscopic properties of 1.32 μm band fluorescence. It is shown that the introduction of an appropriate amount of WO₃oxide can effectively improve the 1.32 μm band fluorescence intensity through the enhanced multi-phonon relaxation (MPR) processes between the excited levels of Nd³⁺. The results indicate that the prepared Nd³⁺-doped tellurite glass with an appropriate amount of WO₃oxide is a potential gain medium applied for the O-band broad and high-gain fiber amplifier.