A diverse array of amino- and alkoxybenziodoxoles can be easily synthesized by reacting the respective amines and alcohols with chlorobenziodoxole. These iodane compounds undergo insertion of arynes into the N−I(III) and O−I(III) bonds to give ortho-amino- and alkoxy-arylbenziodoxoles, the iodane group of which can be leveraged as a versatile leaving group for downstream transformations.