We report an efficient radical-based and photocatalyst-free method for the C(sp2)-C(sp3) cross-coupling reaction to synthesize α-aryl ester derivatives. The process starts from a β-keto ester and an electron-deficient halogenated aryl halide under alkaline conditions to form an electron donor-acceptor complex and is driven by visible light. From the synthetic point of view, this newly established method represents a simple way to access arylpropionic acids from commercially available and cheap starting materials.