The bismuth-doped α-BBO single crystals were prepared by traditional Czochralski method in ambient atmosphere, and the obtained samples were irradiated by γ-ray . The absorption, emission and fluorescence decay curves were measured at room temperature. Near-infrared super-broadband emission (FWHM ~113 nm) of Bi:α-BBO single crystal subjected to γ-irradiation was observed to be center-peaked at ~1139 nm upon 808 nm excitation. The effect of irradiation and annealing treatment on the emission was discussed, and the mechanism for the wide emission band was investigated preliminarily.