Laser induced fluorescence spectrum of NiBr in the visible region between 604 and 666nm has been recorded and analyzed. Fourteen bands belonging to three electronic transition systems, namely, [15.1]Δ5∕22–XΠ3∕22, [15.1]Π3∕22–XΠ3∕22, and [14.0]Δ5∕22–XΠ3∕22 have been observed. Spectra of isotopic molecules were also observed and analyzed. Detailed analysis of the recorded spectra indicated that the two electronic states [15.1]Π3∕22 and [15.1]Δ5∕22 lie about 1cm−1 apart from each other and J-dependent perturbation due to spin-uncoupling interaction has been observed. Least squares fitting procedures involving deperturbation matrix elements were used to fit the observed line positions, which yielded accurate molecular constants for the [15.1]Π3∕22 and [15.1]Δ5∕22 states. In addition, the (1,0) band of the [15.1]Δ5∕22–XΠ3∕22 transition shows partially resolved hyperfine structure that was caused by the interaction of unpaired electron with the magnetic moment of the Br nucleus (nuclear spin of I=3∕2) in the excited state. The rapid decrease in hyperfine width as J increases suggests that the hyperfine coupling in the excited state conforms to Hund’s case (aβ) coupling scheme.