To demonstrate the utility of the novel reagents, wellestablished methods for transition metal-free arylation of various nucleophiles with diaryliodonium salt 3a were utilized to provide a range of ortho-substituted azobenzene products. The transformations proceeded with complete chemoselectivity and retained E-configuration (Scheme 3). O-Arylation of phenol and carboxylic acids delivered the azobenzenefunctionalized diaryl ether 4 and aryl esters 5, 6 in good yields. The aryl ester 6 could be hydrolyzed under mild conditions into 2-hydroxyazobenezene 7 in 81% yield, which has excellent features as structural motif in pharmaceutical and material science. The synthesis of product 7 was also feasible through the hydroxylation of 3a with hydrogen peroxide 36 in moderate yield. As Pd-catalyzed ortho-acyloxylation and hydroxylation of azobenzenes is reported, 21a, 22 we were eager to evaluate the reactivity of 3a with other types of nucleophiles.