The first catalytic regio- and enantioselective aminolysis of 3,4-epoxy alcohols has been accomplished. Under the catalysis of Ni(ClO4)(2)center dot 6H(2)O, the C-4 selective ring opening of various 3,4-epoxy alcohols proceeded in a stereospecific manner with high regioselectivities. Furthermore, with the Ni-BINAM catalytic system the enantioselective ring opening of 3,4-epoxy alcohols furnished various gamma-hydroxy-delta-amino alcohols as products with complete regiocontrol and high enantioselectivities (up to 94% ee).