Dual Ligands Unlocking Iron and Halogen-Containing Carboxylates-based Photocatalysis for Chloro/Fluoro-Polyhaloalkylation of Alkenes Herein, we demonstrate a practical dual ligand-enabled iron photocatalysis paradigm—translating all kinds of halogen-containing carboxylates (CnXmCOO−, X: F, Cl, Br) into CnXm radicals for the valuable chloro/fluoro-polyhaloalkylation of non-activated alkenes with easily available trichloroacetonitrile/Selectfluor as the electrophilic halogenation reagent.