Bismuth-doped glasses and fibers with broadband near-infrared (NIR) emission have garnered much attention on account of their potential applications in new fiber lasers and broadband amplifiers. Yet the realization of high gain from Bi-doped fibers and highly efficient NIR emission from Bi-doped glasses are still a stubborn puzzle. The enhancement of Bi NIR emission is normally based on modifying the glass composition and topology, which will change the structure of the glass over a wide range and alter the thermal or mechanical properties of the glass simultaneously, making it more complicated for the designing and fabricating of Bi fibers with good performance. Here, we find that a trace addition of Si3N4 can efficiently enhance the Bi NIR emission without changing the glass structure significantly, right followed by spectral and structural analysis. Al-27 NMR measurement reveals that the short- to medium-range order of this glass is unchanged. The EPMA measurement confirms the homogeneity of fabricated glass. The great enhancement and red-shift under blue light excitation may originate from the conversion of Bi active centers to low valence. Our results indicate that the trace addition of nitride could be a facile and maneuverable way to control the valence of active ions in glasses, which may contribute to improving the performance of photonic glasses.