The selective defluorofunctionalization of fluoroarenes via transition-metal catalysis has garnered significant attention. This study presents an amine-controlled, directing-group-assisted strategy to achieve selective hydrodefluorination and defluoroamination of fluoroarenes. Dimethylamine enables the selective hydrodefluorination of fluoroarenes through β-hydride elimination from a nitro-centered nickel intermediate, while other amines furnish the defluoroamination reactions. In hydrodefluorination, dimethylformamide (DMF) serves a dual role as both the solvent and the source of dimethylamine. These reactions demonstrate high selectivity and a broad substrate scope.