The importance of fluoroalkyl groups connected to oxygen has been highlighted owing to their remarkable role in tuning various properties of organic molecules. We have developed a practical visible-light-induced (hetero)aryloxytetrafluoroethylation of heteroaromatics and alkenes under mild conditions. Two functional groups consisting of oxygen and fluoroalkyl moieties could be simultaneously installed into unactivated heteoaromatics and alkenes. In addition, the high diversity on both substrates and oxyfluoroalkyl reagents make this a useful method for late-stage modifications in the development of various functional molecules, including drug molecules.