Multicomponent reactions represent a powerful method for building complex molecules from structurally simple starting materials. Herein, we report a novel three-component radical-polar crossover reaction involving a tandem addition reaction of two different olefins, which is initiated by the selective addition of fluorosulfonyl radicals to alkyl alkenes. This tandem process provides facile and effective access to multiple functionalized aliphatic sulfonyl fluoride molecules. Further transformation of the products is also demonstrated.