In order to obtain the tellurite glass with good thermal stability and high-intensity luminescence, WO₃ is doped into the TeO₂-ZnO-Na₂O system to improve the anti-devitrification and thermal stability of the glass. The results show that the ΔT of the tellurite glass increases from 110 °C without WO₃ to 142 °C with WO₃ content of 20 mol%. On the basis of thermal stability study of tellurite glass, the spectral properties of single-doped Er³⁺ and Er³⁺/Yb³⁺ co-doped tellurium tungstate glasses are further studied. The research results show that under the co-doping conditions of Er³⁺/Yb³⁺, the energy transfer between Er³⁺/Yb³⁺ improves the absorption efficiency of Er³⁺ ions for 980 nm pump light, and the luminescence intensity in the 1.5 μm band is enhanced. Finally, Er³⁺/Yb³⁺ co-doped tellurium- tungstic glass with high-intensity 1.5 μm band emission is obtained, indicating that the co-doping of Er³⁺/Yb³⁺ is an effective method to achieve high-intensity luminescence in the 1.5 μm band.