Epoxides undergo smooth ring-opening with aryl amines in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim] BF4) or 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim] PF6) ionic liquids under mild and neutral conditions to afford the corresponding β-amino alcohols in excellent yields with high regioselectivity.