A new method of synthesizing graft copolymers having a poly(perfluoroalkylethyl methacrylate) (PFMA) backbone has been suggested and illustrated by preparing poly(perfluoroalkylethyl methacrylate)-g-poly(methyl methacrylate)s (PFMA-g-PMMA). These copolymers were prepared using the macromonomer technique and emulsion copolymerization method. PMMA macromonomers were synthesized by acylation of hydroxyl-group terminated PMMAs which were prepared by radical oligomerization of methyl methacrylate with a chain-transfer agent. The PMMA macromonomer was copolymerized with a comonomer of perfluoroalkylethyl methacrylate (FMA) by emulsion polymerization to obtain graft copolymers of PFMA-g-PMMA. Toluene was chosen as a suitable solvent to obtain stable emulsions containing PMMA macromonomer and FMA for copolymerization. Graft copolymers having various PMMA compositions and branch lengths could be prepared. It is confirmed that the desired graft copolymers were successfully prepared and that the method suggested for synthesizing PFMA-g-PMMAs is useful in the manufacture of various surface modification agents.