In conclusion, the synthesis of ortho-azobenzene-derived diaryliodonium salts could be achieved in high yields, despite the challenges associated with ortho-functionalization of azobenzenes. The novel iodonium reagents were demonstrated as chemoselective arylation reagents with a wide range of C, N, O and S-nucleophiles under mild and metal-free conditions, to give even sterically hindered products. The X-ray crystal structure revealed that the nitrogen is involved in hypervalent bonding with the iodine(III) center. To our delight, the photoswitching properties of the azobenzene were retained in the hypervalent azobenzene derivatives. Using UV (340 nm) and visible (450 nm) light, the isomerization between E-and Zisomer was reversible. The incorporation of the hypervalent iodine bond influenced the position of the absorption maxima and drastically reduced the half-life time.