PMMA homopolymer with CF₃(CF₂)₂CF₂- end group was prepared by the ATRP of MMA using CF₃(CF₂)₂CF₂-I as an initiator and copper(I) salts/bipy catalysts. This indicated the production of perfluorobutyl radicals by ATRP mechanism and successful polymerization by them. Di- and triblock copolymers were also prepared by the ATRP of MMA using iodine-terminated PVDF as (macro)initiators. The kinetic plots (ln[M]_o/[M] vs. time) showed nearly first-order with respect to monomer concentration and the M_n,NMR of block copolymers increased linearly with conversion. However, iodine-terminated PVDF showed low initiator efficiency because propagating rate was much faster than initiating rate