We report here a cascade process integrating the hexadehydro Diels–Alder (HDDA) reaction with alkynyliodanation, enabling efficient synthesis of highly substituted aryl-λ3-iodanes. Heating a mixture of a tetrayne and an alkynylbenziodoxole induces regioselective insertion of the tetrayne-derived aryne into the alkynyl–iodine(III) bond, yielding a 1,4-dialkynyl-2-iodanyl-3-aryl(or alkyl)benzene derivative. The unique regiochemistry facilitates subsequent π-extension, allowing divergent access to polyaromatic frameworks, such as helicenes and cyclopenta[cd]pyrenes, underscoring the utility of aryne carboiodanation in complex aromatic synthesis.