As a new member of laser glass family, bismuth-doped glasses have received rising interests due to the application of fiber amplifiers and laser sources in the new spectral range for the next-generation optical communication system. For practical application of the glasses, it must be considered on how to improve the luminescence efficiency. Here, we demonstrate that addition of aluminum can enhance the bismuth near-infrared luminescence by more than 10 000 times, which is right followed by the discussion on the mechanism on why this can happen. We believe this work can be helpful for designing bismuth-doped multiple component laser glasses with high efficiency. In addition, because of high susceptibility of bismuth to local field change, it can be used as probe ion to envision glass structures. Using bismuth as a luminescent structural probe, we can see the modifier ions of Bi+ are not completely randomly distributed inside germanate glass and they prefer the residence around tetrahedral AlO4 sites.