Block copolymers consisting of a pentafluorostyrene (PFS) block and a hydrophilic block were synthesized by RAFT polymerisation. The hydrophilic blocks consist of methacrylate derivatives, 4-hydroxystyrene or 4-vinylpyridine monomers. The block copolymers were obtained with narrow molecular weight distributions and the molecular weights were in good agreement with the theoretical values. In addition, a model thiol was reacted with the PFS moieties of the block copolymers. This polymer-analogous reaction was performed under ambient conditions in high yields resulting quantitatively in para-substitution of the pentafluorophenyl rings. Finally, thin films consisting of block copolymers that showed strong phase-segregation behaviour and ordered nanostructured surfaces consisting of both blocks were obtained. (C) 2010 Elsevier Ltd. All rights reserved.