A thioether-containing hyperbranched polyglycerol (PG) was synthesized by a simple and effective two-step reaction; first a part of the hydroxyls of PG was transformed to carbamates by the reaction with the highly reactive 2-chloroethyl isocyanate, and then the chlorine group was S-alkylated with HS(CH2)(n)OH (n = 2, 6, 11). The resulting PGs with various molecular weights were successfully used as template for synthesis of nanoscale cadmium chalcogenide quantum dots (QDs). It was found that the size of these QDs was dependent on the polymer template. Moreover, after solvent evaporation, the polymer was assembled into large cluster, and a variety of morphologies were formed by the cluster inside the QDs. (c) 2006 Wiley Periodicals, Iric.