The direct conversion of a C(sp²)–F bond into the corresponding C(sp²)–C(sp³) bond using Al(alkyl)₃ as the coupling partner under nickel catalysis is reported. Intriguingly, aryl fluorides, alkenyl monofluorides, and alkenyl gem-difluorides are viable electrophiles in this transformation, constituting the notable feature of this protocol. The success of this chemoselective method relies on the fluorophilicity of the employed aluminum reagent that functions as both the Lewis acid for the activation of the challenging C–F bond and the corresponding alkylating partner. Successful application of this strategy to the late-stage C–F alkylation of fluorinated drug analogue is also demonstrated. This method represents another important example of using challenging C–F bonds as alternative electrophiles.