A chemically unprotected mannose-containing acrylate (ManA) monomer was synthesized and polymerized by Cu(0)-mediated radical polymerization in water (SET-LRP). One-pot block copolymerization was achieved upon addition of a solution of N-isopropylacrylamide (NIPAm) or diethylene glycol ethyl ether acrylate (DEGEEA) forming thermoresponsive double hydrophilic diblock glycopolymers which revealed self-assembly properties in aqueous solution forming well-defined, sugar-decorated nanoparticles.