Bismuth (Bi)‐doped laser glasses with broadband emission are of current interest in the fields of sensing, bio‐imaging, and photonics. For practical applications, it must be considered how to improve the emission efficiency, in particular, for borate glasses with wide glass‐forming range, low melting point, and excellent fiberizing ability. Herein, we experimentally demonstrate that addition of GeO2 to aluminoborate glasses can effectively enhance Bi NIR emission by more than 300 times with prolonged decay time (~500 μs) and good homogeneity, which is, to our best knowledge, seldom achieved in Bi‐doped borate multi‐component glasses. The addition of second glass‐former GeO2, as revealed by detailed optical and structural analysis, leads to the facile regulation on local glass structure, forcing the conversion of aluminum species from AlO5 and AlO6 to AlO4 and consequently pushes the conversion of Bi3+ to Bi+ and Bi0 and stabilizes Bi NIR centers, which finally results in highly enhanced Bi NIR emission. We believe these results could contribute to designing Bi‐activated multi‐component laser glass and fibers with efficient NIR photoemission.