A practical synthesis of unique, precisely decorated, multisegmented block copolymers was elaborated via amine-thiol-ene conjugation. By mixing the thiolactone-acrylate heterotelechelic precursor polymer with selected amines, a library of multisegmented species was obtained, featuring a high level of control over backbone structure and spatial arrangement of side chain residues. Ranging from glycosylated to amphiphilic materials, these macromolecular lineups have been analyzed by LCxSEC DOSY-NMR, and DLS, revealing the particular properties of these macromolecular structures.