Herein, an electron donor-acceptor complex (EDA)-enabled photoredox nickel-catalyzed coupling/controllable defluorination domino sequence has been successfully developed, providing an efficient route to a series of α-fluoroarylacetic esters and amides. This methodology accommodates a diverse array of commercially available aryl bromides and chlorodifluoroaryl carboxylic acid derivatives as suitable substrates. Preliminary mechanistic investigations suggest that the reaction is initiated by photoinduced EDA-enabled/nickel-catalyzed direct cross-electrophile coupling, with further defluorination proceeding through the generation of EDA complexes, facilitating a controllable reductive defluorination process.