unsymmetric aromatic azocompounds through an efficient and cross-selective oxidative dimerization of aromatic amines using tert-butyl hypoiodite (t-BuOI) under metal-free and mild conditions has been developed. This method was also found applicable to the synthesis of heteroaromatic azocompounds. The spectroscopic study indicates the involvement of N,N-diiodoanilines in the oxidative reaction as the key