A series of novel âjellyfishâlikeâ graft copolymers with chitooligosaccharide (COS) as shorter backbone and poly(Δâcaprolactone) as longer branches were synthesized using ringâopening polymerization of Δâcaprolactone via a protectionâpolymerizationâdeprotection procedure with trimethylsilylchitooligosaccharide as intermediate and triethylaluminum as catalyst precursor. The obtained chitooligosaccharideâgraftâpoly(Δâcaprolactone) polymers possess amphiphilic structure with hydrophilic COS backbone and hydrophobic polycaprolactone branches. Because of this unique âjellyfishâlikeâ structure, these graft copolymers could selfâassemble to form various morphologies of aggregates in a mixture solution of water and tetrahydrofuran. The transmission electron microscopy studies revealed that the formed aggregates exhibited necklaceâlike, flowerâlike onion vesicle, and tubular morphologies. It is found that the hydrogenâbonding formed by the hydroxyl and amino groups remained on the COS backbone played an important role during the aggregation of these graft copolymers, and their morphologies were changed with the varying length of poly (Δâcaprolactone) branches, the concentration of the graft copolymer, and the selfâassembly process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4889â4904, 2008