The poly(methyl methacrylate)-b-poly(2-[[[[2-(perfluorohexyl)]-sulfonyl]-amino]ehthyl]methacrylate) (PMMA-b-PC(6)SMA) copolymers were successfully synthesized for the first time using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) method. Under optimized reaction conditions, the degree of polymerization (DP) of resulting copolymers increased approximately linearly with monomer conversion. Structures of a well-defined block copolymer were determined by GPC, FT-IR, and H-1-NMR spectra. Results from AFM and contact angle measurements of polymer films revealed the presence of block segments derived from PC(6)SMA, as indicated by the obvious increase in hydrophobicity and oleophobicity. The relationship between surface composition and surface wetting ability was confirmed by XPS and AFM spectra. Compared with the random copolymer PMMA-co-PC(6)SMA, C(6)SMA dosages in the PMMA-b-PC(6)SMA copolymers were greatly decreased, which retained its hydrophobic and oleophobic properties. (C) 2016 Wiley Periodicals, Inc.