The strategic generation of α-fluoro radicals underpins powerful routes to fluorine-rich architectures of high value in molecular design. Here, we disclose an operationally simple, catalyst-free method for the photochemical activation of α-halo fluorinated precursors using visible light and two inexpensive additives, sodium iodide and 2,6-lutidine. This mild protocol enables in-situ halide exchange and subsequent homolytic C–I bond scission to generate α-fluoro radicals under ambient conditions. The generality of the platform is demonstrated across esters, sulphones, and nitriles, facilitating intermolecular coupling with alkenes, heteroarenes, and propellanes to access diverse fluorinated scaffolds. Mechanistic studies support the formation of a weak electron donor–acceptor complex that mediates bond activation, while the benign conditions permit merger with energy transfer catalysis for stereodivergent product formation.