A metal-free regio- and stereoselective method is achieved for the preparation of ( E)-configured α-halo enamides, vinyl thioethers, and vinyl ethers using aqueous HX (X = F, Cl, Br, I), which features high functional group compatibility and regio- and stereoselectivity, mild conditions, high efficiency, and rapid transformation. Additionally, the isomers could be yielded readily from the ( E)-configured α-halo enamides via photocatalysis or under Sonogashira coupling conditions.