Biodegradable star-shaped poly(epsilon-caprolactone) (PCL) with four arms were synthesized by ring-opening polymerization (ROP) from a symmetric pentaerythritol core via the "core-first" strategy. Subsequently, two samples of the amphiphilic A(4)B(8) star-block copolymers with symmetrical topologies [4s(PCL-b-2sPEG)] were synthesized by a macromolecular coupling reaction between carboxyl-terminated poly (ethylene glycol) (PEG) and 4-arm star-shaped PCL macromers with eight -OH end groups. The latter was prepared by attaching 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid (HHMPA) to 4sPCL using a simple two-step reaction sequence. The in vitro cytotoxicity test indicated no apparent cytotoxicity. The amphiphilic star-block copolymers are capable of self-assembling into spherical micelles in water at room temperature, and they possess low critical micelle concentrations (CMCs) of 2 similar to 8 mg/L in aqueous solution which was determined by fluorescence spectroscopy using pyrene as a probe. Transmission electron microscopy (TEM) measurement demonstrated that the micelles exhibit a spherical shape with a size range of 30 similar to 50 nm in diameter. In addition, the hydrophobic and anticancer drug, quercetin, is loaded effectively in the polymeric micelles, suggesting that these new materials are appropriate candidates as hydrophobic drug nanocarriers. (c) 2011 Elsevier Ltd. All rights reserved.