Glycopolymers consisting of styrene (St) and pentafluorostyrene (PFS) were synthesized by a combination of nitroxide-mediated polymerization and "click" chemistry. A series of well-defined homopolymers as well as block and random copolymers of St and PFS were obtained with different ratios by using Bloc Builder as an alkoxyamine initiator. Some copolymers showed self-assembly behavior into regular nanospheres with diameters ranging from 70 to 720 nm by applying the nanoprecipitation technique. In addition, a thiol-glycoside (2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranose) was reacted under ambient conditions with PFS moieties on the polymeric backbone utilizing a thiol-para fluoro "click" reaction. This. nucleophilic substitution reaction was performed with high yields, and the reaction kinetic was monitored online with F-19 NMR spectroscopy. Finally, the deacetylation of the protected glucose moieties was carried out to yield well-defined glycopolymers. The polymers were characterized in detail by H-1, C-13, and F-19 NMR spectroscopy, size exclusion chromatography, and MALDI TOF-MS.