A new approach for highly regioselective iodination of azobenzenes with alkyl iodide as the iodinating reagent enabled by Rh-catalyzedoxidativeC–Hactivation has been developed. By changing the oxidant, various mono- and di-iodinated azobenzenes were smoothly obtained in moderate to excellent yields, respectively. The preliminary mechanistic study reveals that the reaction process might undergo electrophilic