Electronic and luminescence characteristics of Bi/Al co-doped silica optical fiber model were investigated by using first-principle methods. Our results show that the preference Al substitution site is the adjacent Si site rather than O site. The doping of Al can contribute to the dispersion of Bi[Formula: see text] luminescence center and generate new luminescence center at [Formula: see text]1100 nm by affecting [Formula: see text] orbital of the O atom near Bi atom. Our results give a possible explanation of the near-infrared (NIR) luminescence in Bi/Al co-doped silica optical fibers.