This paper describes the synthesis of bio-based methacrylated 12-hydroxystearate glucose (MASG), and its (co)polymerization with methyl methacrylate (MMA) by either free- or RAFT radical polymerizations. The obtained amphiphilic p(MMA-MASG) copolymers self-assembled in water into various morphologies depending on the MASG unit content and glycopolymer crystallinity. Finally, as a proof of concept, a hydrophobic dye, Nile Red, was entrapped by co-nanoprecipitation into p(MMA-MASG) nanoparticles, showing their loading capacity and thus demonstrating the potential of such amphiphilic glycolipid-based copolymers in hydrophobic compound encapsulation applications.