Upon irradiation with UV light of 340 nm, both molecules switched to the corresponding Z-isomer (E/Z ratio PSS340: 32/68 (1a), 29/71 (3a)). The re-isomerization to the E-isomer occurred upon irradiation with visible light of 450 nm (E/Z ratio PSS450: 90/10 (1a), 72/28 (3a)). A complete conversion to the E-isomer could not be achieved photochemically. However, no significant photodegradation was detected for 1a and 3a upon repeating switching. The incorporation of the hypervalent moiety had almost no influence on the absorption maxima of the azobenzene switch: * transition at 325 nm (1a) vs. 338 nm (3a) and n* transition at 434 nm vs. 436 nm (3a). However, the half-life time was significantly decreased: t1/2 124.6 h (1a) vs. 5.83 h (3a). This can be attributed to the strong electron acceptor character of the iodine(III) moiety, and the N-I stabilizing interaction observed only in the (E)-isomer.