A variety of poly(ε-caprolactone)-grafted dextran copolymers were synthesized with a controlled architecture through a three-step procedure: partial protection of the dextran hydroxyl groups by silylation, ring-opening polymerization of ε-caprolactone initiated from remaining free hydroxyl groups on partially silylated dextran, and silyl ether deprotection under mild conditions. The potential of these amphiphilic grafted copolymers as surfactants was investigated by water/toluene interfacial tension measurements. Since each copolymer showed noticeable sur-factant properties, their ability to form 'surfactant-free' nanoparticles was evaluated using the nanoprecipitation method. It was found that remarkably stable core (poly-ester)-shell (polysaccharide) nanoparticles with a mean diameter around 200 nm were formed.