Aminocarbonylation of aromatic iodides with CO and amines gives aromatic amides under photoirradiation conditions. DFT calculations predict that methylamine adds to benzoyl radical to give a zwitterionic radical, which would afford the product via two pathways: (a) an amine-assisted proton transfer followed by a single electron transfer reaction (SET) with iodobenzene or (b) complexation with iodobenzene and then the SET.