The selective activation of C-H bonds under mild Rh-III catalytic conditions has been developed for the perfluoroalkenylation of various cyclic and acyclic aromatic ketones. This protocol uses versatile reagents and mild conditions. It requires a very low catalyst loading and has exceptional functional group tolerance as well as provides products in good to excellent yields. An application of this approach was described for the preparation of perfluoroethyl acrylate derivatives of biologically active substances.