Novel fluorinated associative copolymers poly(ethylene glycol)-b-poly(2-(perfluorohexyl)ethyl methacrylate (PFHEMA)-co-3-[N-(2-methacroyloylethyl)-N,N-dimethylammonio]-propane sulfonate (DMAPS)) (PEG-b-PPFHEMA/PDMAPS) were prepared as a type of non-viral gene vector. The series of PEG-b-PFHEMA/DMAPS with different molecular weights and compositions were characterized by gel permeation chromatography-multi-angle light scattering, H-1 NMR, F-19 NMR, and elemental analysis. The interactions of the copolymers with calf thymus DNA and the morphologies of the resulting complexes were studied by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. In addition, the DNA-polymer interaction, as determined by the gel retardation assay, and the low cytotoxicity of PEG-b-PPFHEMA/PDMAPS demonstrated that these copolymers have good DNA binding capacity and potential for high performance in the practical application of DNA delivery. Crown Copyright (C) 2013 Published by Elsevier Ltd. All rights reserved.