Ca(CF3CO2)2 efficiently catalyzed the selective ring-opening of epoxides by amines leading to the synthesis of β-aminoalcohols. The reaction works well with various aromatic and aliphatic amines under solvent-free conditions. Corresponding β-aminoalcohols were obtained in excellent yields with high regioselectivity. The catalyst was easily prepared by reaction of CaH2 in trifluoroacetic acid.