Triblock copolymers of poly(dimethylsiloxane) (PDMS) middle block and degradable polyester end blocks were synthesized by the ring open polymerization initialed by alcohol groups of PDMS. Surface composition of the triblock copolymers is measured by angle-dependent electron spectroscopy for chemical analysis. The PDMS blocks are segregated in the topmost surface region and constituted up to 90 mol% of the surface, even though the overall bulk PDMS concentrations of the block copolymers is 6% or less. This result suggests that the bulk property of degradable polyesters is essentially unchanged due to the high surface segregation of PDMS.