In this paper, a novel air-stable triphenylbismuth bisperfluorooctanesulfonate was synthesized by treatment of moisture-sensitive triphenylbismuth dichloride with silver bisperfluorooctanesulfonate in anhydrous CH 2 Cl 2 at room temperature. Its catalytic assessment results show that the reactions of arylamine and epoxide proceed efficiently in the presence of triphenylbismuth bisperfluorooctanesulfonates 1 (5.0 mol%) under solvent-free condition, affording β-amino alcohols in good to excellent yields. The yields of desired products do not reduce obviously after recycling for 4 times of catalyst 1. Hence, a convenient and efficient method for preparation of β-amino alcohols is provided.