Bi:α-BaB2O4 crystal samples are grown by the traditional Czochralski method and the obtained samples are irradiated by electron beam. Absorption and emission spectra of the samples are measured at room temperature before and after their electron irradiation. Under 808 nm LD excitation, broadband (FWHM at 52 nm) near-infrared emissions centered at about 1135 nm are observed in electron-irradiated Bi:α-BaB2O4 samples. Both the emissions are believed to be due to Bi+ ions. Electron beam helps to reduce Bi3+ and Bi2+ into univalence. The formation processes in the samples with different radiation doses are not the same, which is primarily discussed in this work.