<p>Bi-doped glass fibers with controllable optical response are essential for next-generation broadband amplifiers and tunable lasers. However, achieving broad wavelength tunability and stable near-infrared (NIR) emission remains challenging due to limited structural modification of conventional silica glasses and variability of Bi active centers (BACs). Here, we propose a cation hybridization strategy to overcome these issues, demonstrating an enhanced ultra-broadband, multi-band NIR optical response in Bi-doped photonic glasses. Alkaline earth metal ions, such as Mg²⁺ and Ba²⁺, were employed as the hybrid cations to “repair” (Mg²⁺) and “tailor” (Ba²⁺) the flexible glass network of germanate glasses, enabling precise customization of the local environment to stabilize different BACs. Impressively, this enables a tunable optical response, ranging from one main peak emission at 1142 nm to a stable multi-band emission spanning 920, 1142, 1265, and 1516 nm, with an emission bandwidth of 526 nm, which is distinct from conventional rare-earth ions doped glasses. Furthermore, Bi-doped hybrid germanate glass fibers were fabricated and a positive on-off gain in multiple communication bands (O + E + S + C bands) was successfully achieved. The results offer new insights into the Bi NIR luminescence behavior and introduce a promising strategy for developing advanced photonic glass materials.</p>