The development of a novel intermolecular oxidative C-H alkoxylation of aniline derivatives is described under metal-free conditions with high reaction rates at ambient temperature. In the presence of an I(III) oxidant, a range of aldehydes, anilines, and alcohol substrates undergo three-component coupling to produce synthetically useful alkoxyl-substituted N-arylimines. The preliminary mechanism investigations revealed that the transformation proceeds via imines as intermediates.