The Er³⁺/Ce³⁺co-doped tellurite-based glasses (TeO₂-Bi₂O₃-TiO₂) modified with various WO₃contents are prepared using conventional melt-quenching technique. The X-ray diffraction (XRD) patterns and Raman spectra of glass samples are measured to investigate the structures. The absorption spectra, the up-conversion emission spectra, the 1.53 μm band fluorescence spectra and the lifetime of Er³⁺:⁴I_13/2 level are measured, and the amplification quality factors of Er³⁺are calculated to evaluate the effect of WO₃contents on the 1.53 μm band spectroscopic properties. With the introduction of WO₃, it is found that the prepared tellurite-based glasses maintain the amorphous structure, while the 1.53 μm band fluorescence intensity of Er³⁺is improved evidently, and the fluorescence full width at half maximum (FWHM) is broadened accordingly. In addition, the prepared tellurite-based glass samples have larger bandwidth quality factor than silicate and germanate glasses. The results indicate that the prepared Er³⁺/Ce³⁺co-doped tellurite-based glass with a certain amount of WO₃is an excellent gain medium applied for the 1.53 μm band Er³⁺-doped fiber amplifier (EDFA).