Experimental and theoretical studies of spectral properties of crystalline TlCl:Bi are performed. Two broad near-infrared luminescence bands with a lifetime of about 0.25 ms are observed: a strong band near 1.18 μm excited by 0.40, 0.45, 0.70, and 0.80 μm radiation and a weak band at ≳1.5 μm excited by 0.40 and 0.45 μm radiation. Computer modeling of Bi-related centers in TlCl lattice suggests that a Bi(+)…VCl(Cl)(-) center (Bi(+) in Tl site and a negatively charged Cl vacancy in the nearest anion site) is most likely responsible for the IR luminescence.