The metal-catalyzed aminohydroxylation is a powerful method for the stereo-controlled construction of β-amino alcohols. However, very few intermolecular aminohydroxylations have been reported to date. This short review provides a recent development of the intermolecular copper- or iron-catalyzed oxaziridine-mediated aminohydroxylation of styrenes with high regio- and enantioselectivity.