We report here a photoinduced iron-catalyzed fluoroalkylation-peroxidation of activated and/or unactivated alkenes with fluoroalkyl carboxylic acids and hydroperoxide. The ligand-to-iron charge transfer strategy effectively overcomes the high redox potential of the fluoroalkyl carboxylic acids, facilitating the difunctionalization reaction to occur smoothly under mild reaction conditions. The late-stage functionalization of drug and natural product derivatives was also demonstrated.