Bismuth (Bi)‐doped glass and fiber materials exhibit excellent optical performance and have potential in fields such as fiber communication and tunable lasers. However, the preparation of Bi‐doped glass and fiber with high optical activity is still confronted with huge challenges. This study proposes a germanium oxide hybridization strategy to enhance near‐infrared emission in Bi‐doped glass. In addition, by the systematical optimization of the optical response and processability of the glass system, Bi‐doped glass fibers are successfully constructed. The constructed glass fibers have excellent optical performance, and the enhanced amplified spontaneous emission is realized. They show potentials for applications in broadband fiber amplifiers and tunable lasers.