The first catalytic regioselective and stereospecific halogenation of 2,3-epoxy alcohols and 2,3-epoxy sulfonamides has been developed. Under the catalysis of commercially available W- or Mo-salts, complemented by the method using cerium halides, the C-3 selective ring opening of structurally diverse epoxides with Cl-, Br-, and I-nucleophiles afforded various halohydrins in good yields and high regioselectivities.