Experimental and computer-modeling studies of the spectral properties of crystalline AgCl doped with metal bismuth or bismuth chloride are performed. The broad near-IR luminescence band in the 0.8-1.2 μm range with time dependence described by two exponential components corresponding to the lifetimes of 1.5 and 10.3 μs is excited mainly by 0.39-0.44 μm radiation. Computer modeling of probable Bi-related centers in the AgCl lattice is performed. On the basis of experimental and calculation data, a conclusion is drawn that IR luminescence can be caused by Bi+ ion centers substituted for Ag+ ions.