An operationally simple and practical method is disclosed to achieve the difunctionalization of styrenes, generating fluorinated benzyl bromides via a photoinduced atom transfer radical addition process. The developed method is mild, atom-economical, cost-effective, employs very low photocatalyst loading (1000 ppm), and is highly compatible with a broad range of functional groups on styrene. The versatility of the fluorinated benzyl bromides is demonstrated through their derivatization to a variety of valuable compounds.