Because of ultra-broadband near-infrared (NIR) emission bismuth-activated glasses and fibers offer a new promising platform for novel photonic devices such as new type of optical amplifiers and broadly tunable fiber lasers. Yet, challenge remains to manipulate the NIR emission behavior of bismuth (Bi) in photonic glasses for efficient Bismuth-doped fiber and fiber lasers. Here, by engineering phosphorus and aluminum's topology, broadly tunable NIR emission has been realized in Bismuth-doped phosphate laser glass. Structural and optical analyses on Al-27 magic-angle spinning nuclear magnetic resonance (MAS NMR), P-31 MAS NMR, fourier transform infrared (FTIR) and static emission spectra suggest that polymerization of glass network can be improved by proper addition of aluminum into the system, which can be evidenced by partial conversion of Q(2) to Q(3) species of phosphorus and the shift of P-O-P asymmetric stretching vibration toward lower frequency, and this turns out beneficial to Bi NIR emission. Embedding aluminum tetrahedra into phosphorus glass network can reduce the local crystal field around bismuth and therefore lead to the blueshift of Bi emission. This work presents new insights into the luminescent behavior of Bi ions in phosphate glass and it helps the design and fabrication of Bismuth-doped glasses and fibers in future.