In this study, the correlation between the Raman structure, thermal stability, and mechanical properties of TeO2-ZnO-La2O3–WO3 glasses with varying WO3 contents are systematically established. By exploring the critical point in the transformation process of glass network structural units, the optimal glass components of 74TeO2-12ZnO-5La2O3–9WO3 glass possess the maximum thermal stability (158 °C) and the highest mechanical properties at the same time. The maximum Vicker hardness and Young's modulus of the optimal glass can reach up to 4.007 GPa and 56.212 GPa, which are higher than those of the well-known TeO2-ZnO-Na2O (TZN) and TeO2-ZnO-La2O3 (TZL) glasses. Furthermore, the 0.5 mol% Er3+-doped glass at this critical point (TZLW-0.5Er) exhibits a higher laser figure of merit (54.29 × 10−21 cm2 ms), a larger laser gain bandwidth value (116 nm) and higher emission cross-sections at 1600 nm (2.52 × 10−21 cm2) and 1625 nm (1.06 × 10−21 cm2) than other host glasses. Finally, high-efficiency laser outputs at 1600 and 1625 nm based on TZLW-0.5Er glass fiber are successfully achieved by simulation. These results show the greater practical potential of TZLW-0.5Er glass with higher mechanical strength compared to TZN and TZL fibers for the 1.6 μm-band laser.