Bismuth (Bi)-doped near-infared (NIR) glass that can cover the entire optical communication window (850, 1310, and 1550 nm) has become the subject of extensive research for developing photonic devices, particularly, tunable fiber lasers and ultrabroadband optical amplifiers. However, the realization of highly efficient NIR luminescence from Bi-doped glass is still full of challenges. Notably, due to the co-existence of multiple Bi NIR centers in the glass, the origin of newly generated Bi NIR emission peaks at ∼930 and ∼1520 nm is still controversial. Here, we report a new Bi-doped nitridated germanate glass with tunable ultrabroadband NIR emission (850–1700 nm) and high external quantum efficiency (EQE) of ∼50%. A series of studies, including spectral analysis, nuclear magnetic resonance (NMR), and others, provide powerful evidence for the mechanism of luminescence enhancement and tunability, and make reasonable inferences about the origin of the new emission bands at ∼930 and ∼1520 nm. We believe that the results discussed above would enrich our understanding about multiple Bi NIR emission behaviors and contribute to the design and fabrication of highly efficient Bi-doped ultrabroadband wavelength-tunable optical glass fiber amplifiers and lasers in the future.