Bismuth-doped (Bi) glasses and fibers have raised considerable attention for broadband emission and tunable fiber lasers in the near infrared (NIR) region. However, they suffer from low efficiency and it remains challenging to enhance Bi NIR emission. Here, we propose a facile way to enhance and tune the Bi NIR emission by adjusting optical basicity and modulating the boron and aluminum coordination in borate glasses. We find that BO4 and AlO5 species favor Bi NIR emission, right followed by the analyses of static emission spectra, the Fourier transform infrared (FT-IR), and nuclear magnetic resonance (NMR) spectroscopy. Furthermore, abnormal Bi NIR luminescence phenomenon and boron anomaly were observed, which are attributed to the synthetic effect of B and Al coordination transformation. Besides, we find that BO4 tetrahedron plays a major role in enhancing Bi NIR emission at low Al content, while AlO5 hexahedron group will dominate at high Al concentration. Our investigation may give an insight into the luminescent behaviors of Bi in borate glasses and contribute to improving the performance of Bi-doped fiber and fiber lasers in future.