Hexakis[p-(hydroxylmethyl)phenoxy]cyclotriphosphazene was synthesized by the reaction of hexachlorocyclotriphosphazene with the sodium salt of 4-hydroxybenzaldehyde and subsequent reduction of aldehyde Groups to alcohol groups by using sodium borohydride. This compound was employed in initiating the ring-opening polymerization of epsilon-caprolactone and L-lactide to produce star-shaped poly(L-lactide) (PLA), poly(epsilon-caprolactone) (PCL), and their block copolymer with cyclophosphazene cores. H-1 NMR and GPC analysis showed narrow-distributed star-shaped polyesters were successfully synthesized with high yields.