The bromo-terminated small-molecule initiator was prepared by the direct addition reaction of 2,2,3,4,4,4-hexafluorobutyl methacrylate (HFMA) or dodecafluoroheptyl methacrylate (DFMA) with hydrobromic acid in acetic acid under mild conditions. This greatly widened the initiators used for atom transfer radical polymerization (ATRP). The successful polymerization of isobutyl methacrylate (IBMA) or methyl methacrylate (MMA) derived from HFMA-Br or DFMA-Br indicated that fluorinated acrylates could be used as initiators for ATRP. The data of GPC showed the well controlling of the initiator system. FTIR and 1H NMR characterized the structures of the initiators and their polymers. Contact angle measurement indicated that although only one molecule of fluorinated acrylate was introduced, the surface properties of polymers were improved greatly.