A regioselective radical fluoroalkylphosphorylation of unactivated alkenes has been developed by a one-pot twosteps reaction of (bis)homoallylic alcohols, organophosphine chlorides (R2PCl), and fluoroalkyl iodides (RFI) under visible light irradiation. This protocol employs the radical rearrangement of the in situ formed alkoxyphosphane for the first time to regiospecific installing a phosphonyl group onto the inner carbon of terminal olefins in alkene difunctionalization via C-P bond formation

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... and C-O bond homolytic cleavage. Consequently, a series of high value-added fluoroalkylphosphorylated alkyl iodides and alcohols are easily and efficiently synthesized by subsequent iodination and hydroxylation of the generated carbon-centered radicals.