Hexakis[p-(hydroxymethyl)phenoxy]cyclotriphosphazene was prepared by the reaction of hexachlorocycluiphosphaneze with the sodium salt of 4-hydroxybenzaldehyde and subsequent reduction of aldehyde groups to alcohol groups by using sodium borohydride. Hexaarmed star-shaped hydroxyl-terminated poly (F-caprolactone) (PCL) were successfully synthesized via ring-opening polymerization of epsilon-caprolactone (CL) with the above hydroxyl-terminated cyclotriphosphazene initiator and stannous octoate catalyst in bulk. The numberaverage molecular weight of PCL linearly increased with the molar ratio of monomer to initiator. The star-shaped PCL with hydroxy end groups could be used as a macroinitiator for block copolymerization with D,L-lactide (D,L-LA) and glycolide (GA) using stannous octoate catalyst. IR, H-1 NMR and GPC analysis showed the star-block copolymers were successfully synthesized and the molecular weights and the unit composition of the star-shaped block copolymers were controlled by the molar ratios Of D,L-LA and GA monomers to CL. The copolymer presented a two-phase structure, namely, PCL crystalline and D,L-LAGA amorphous domains, which made the copolymer different from linear PCL and star-shaped PCL in crystallinity and thermal behaviors. (C) 2005 Elsevier Ltd. All rights reserved.