Amphiphilic triblock azide copolymers containing poly(ethylene glycol) (PEG) and poly(22,3,4,4,4-hexafluorobutyl acrylate) blocks have been synthesized through room temperature RAFT polymerization using redox initiation and were successfully used to fabricate superhydrophobic cotton fabric by a facile approach. The copolymers were covalently attached to the surface of the cotton fabric by the reaction of azide groups with the cotton fibres based on nitrene chemistry via UV irradiation. Due to introducing the fluorinated polymer chains, the cotton fabric was transformed from hydrophilicity to super-hydrophobicity with a water contact angle of 155 degrees. Since the fluorinated polymer chains were covalently attached on the surface of the cotton fabric, the superhydrophobic cotton fabric possessed high stability and chemical durability. (C) 2010 Elsevier Ltd. All rights reserved.