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-ß-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 19F 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 1H, 13C, and 19F NMR spectroscopy, size exclusion chromatography, and MALDI TOF-MS.