Given the ever‐increasing demand for transmission capacity in optical fiber communication systems, there is a growing focus on developing active fibers and devices with an optical response across a wider spectrum. Bismuth (Bi)‐doped photonic glasses have attracted significant interest for their exceptional ultra‐broadband optical response, particularly within telecommunication bands. However, developing advanced Bi‐activated materials with robust optical response, high compatibility with commercial transmission systems, and low processing temperature remains a huge challenge. Herein, an anion hybridization strategy is proposed to overcome the aforementioned limitations. The anion hybridization significantly enhances the broadband optical response (≈10 times) of the Bi center following the introduction of fluorine ions, and reduces the transition temperature of the photonic glass (≈200 °C). Moreover, the near‐infrared optical response bandwidth experiences significant broadening, a result attributed to the larger inhomogeneous broadening. Furthermore, successful fabrication of the anion‐hybridized Bi‐activated glass fiber is achieved, demonstrating excellent compatibility with commercial transmission fibers. Additionally, the fabricated fiber exhibits an amplified spontaneous emission and on‐off gain across a broad waveband, further validating its efficacy. These results indicate that anion hybridization offers an effective strategy to optimize the optical and thermal properties of photonic materials to develop novel advanced photonic devices.