The chemiluminescence of active nitrogen reaction with CHBr3 was investigated in a flowing afterglow reactor. Strong emission spectrum was observed in the wavelength range from 550 to 750 nm, which is ascribed to NBr(b→X) transition. Meanwhile, in the downstream of the flow tube, emission spectrum exhibits different character dominantly from excited states CN(A, B). The formation mechanism of these excited species has been analyzed, indicating that the generation channel of NBr(b) is from direct N(2D) abstraction bromine from CHBr3, and the excited CN(A, B) comes from the reaction of N(4S) with CBr, which is formed due to CHBr3 dissociation by metastable N2(A).