The combination of a vinyl-substituted aromatic or heteroaromatic and an alkyl bromide or iodide leads, in the presence of Zn and a catalytic amount of an Fe(II) salt, to a net reductive coupling. The new C-C bond is regiospecifically formed at rt at the beta-site of the alkene. The coupling only occurs in an aqueous micellar medium, where a radical process is likely, supported by several control experiments. A mechanism based on these data is proposed.