Herein, a straightforward and efficient approach to iodinated indolo[1,2-c]quinazoline amines via I₂/cumene hydroperoxide (CHP)-promoted cascade annulation of diarylalkynes and isocyanides has been described. This method features excellent regio- and chemoselectivities, good functional group compatibility, and mild reaction conditions. Mechanistic studies suggest that CHP is essential to the catalytic cycle of the reaction. The newly formed indolo[1,2-c]quinazoline scaffolds can be further modified, showing potential applications in medicinal chemistry and materials science.