Cross-coupling chemistry comprises the vast majority of reactions employed in the synthesis of medicines, agrochemicals, and other functional materials. The interest in single-electron-induced coupling chemistry stems from the unique ability of these methods to facilitate the formation of challenging C(sp2)–C(sp3) linkages. This work introduces a new functional group, PT sulfones, for radical cross-coupling, enabling the simplified modular assembly of complex structures in an ordered, practical fashion. The scope of this method is extensively explored, and its strategic application is exemplified through the streamlined preparation of medicinally-oriented fluorine-containing scaffolds that previously required multiple steps, toxic reagents, and non-modular retrosynthetic blueprints. This work has also resulted in the development of five reagents for the rapid assembly of a vast set of structures, many of which contain challenging fluorination patterns.