α-CF₂H substituted amines exhibit improved physicochemical properties and biological performance in pharmaceutically relevant molecules; however, to date, radical difluoromethylation has required expensive preactivated CF₂H reagents and photocatalysts. Herein, we report an iron-mediated ligand-to-metal charge-transfer (LMCT) strategy that enables the direct difluoromethylation of imines generated in situ. Using earth-abundant iron catalysis and inexpensive difluoroacetate salts as a cost-effective CF₂H source, this method affords pharmaceutically relevant α-CF₂H amine structures under mild conditions with decagram-scale scalability.