Trivalent iodine compounds have found widespread applications as oxidants and electrophilic group-transfer agents for organic synthesis. Over the last several years, our group has developed new reactions and synthetic methods of a class of stable trivalent iodine compounds known as benziodoxol(on)es. This article summarizes our studies on (1) new palladium-catalyzed transformations of ethynylbenziodoxol(on)es beyond alkynyl group transfer and (2) the use of benziodoxole triflate as a cationic iodine(III) electrophile for the functionalization of alkynes and arenes, illustrating how the unique reaction chemistry of trivalent iodine can be utilized to achieve synthetically attractive transformations and open up access to previously inaccessible molecular building blocks.