Well-defined polymers with carbohydrate residues pendant to the main chain (glycopolymers) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerisation. Excellent control over molecular weight and narrow polydispersities (1.1-1.2) were achieved over a range of molecular weights. In addition, efficient synthesis of block copolymers by sequential monomer addition with both hydrophilic and hydrophobic non-carbohydrate blocks was demonstrated. The aqueous solution behaviour of amphiphilic block glycopolymers was investigated, revealing the formation of multivalent carbohydrate-bearing aggregates in solution with the capability for the solubilisation of hydrophobic species (a water-insoluble dye). One such amphiphilic glycopolymer shows by TEM the formation of a worm-like micelle phase. Further investigations of these novel bioactive macromolecular assemblies are underway.