Near-infrared (NIR) emitting active centers can exist abundant in Bi:CsI crystal. In addition, Bi:CsI have the simplest crystal structure, body-centered cubic (BCC). In this paper, annealing and quenching treatments were carried out in detail to identify the nature of NIR emitting active centers in Bi:CsI crystals. The changes of absorption and emission spectra with increasing the thermal treatment temperature indicated that the two NIR emission bands at 1210 nm and 1580 nm were related to Bi+ and Bi2 +, respectively. Besides, the assignments of absorption bands and the thermal behaviors of Bi3+, Bi2+, Bi+ and Bi2 + were discussed as well.