Due to the high transparency, high Verdet constant, as well as easy processing properties, rare-earth ion-doped glasses have demonstrated great potential in magneto-optical (MO) applications. However, the variation in the valence state of rare-earth ions (Tb 3+ to Tb 4+ ) resulted in the decreased effective concentration of the paramagnetic ions and thus degraded MO performance. Here, a strategy was proposed to inhibit the oxidation of Tb 3+ into Tb 4+ as well as improve the thermal stability by tuning the optical basicity of glass networks. Moreover, the depolymerization of the glass network was modulated to accommodate more Tb ions. Thus, a record high effective concentration (14.19 × 10 21 / cm 3 ) of Tb ions in glass was achieved, generating a high Verdet constant of 113 rad/(T•m) at 650 nm. Lastly, the first application of MO glass for magnetic field sensors was demonstrated, achieving a sensitivity of 0.139 rad/T. We hope our work provides guidance for the fabrication of MO glass with high performance and thermal stability and could push MO glass one step further for magnetic sensing applications.