1,2-Diiodobenzene is presented as an efficient catalyst precursor for the intermolecular amination of arenes under homogeneous conditions. N-Troc- and N-phthalimido-substituted methoxyamines serve as suitable nitrogen sources providing the corresponding aniline derivatives in up to 99% yield and with up to 66:1 regioselectivity. Key for this successful CN coupling protocol is the strained μ-oxo-bridged conformation of the bisiodine(III) catalyst, which induces unparalleled high reactivity.