When a linear or a four arm star-shaped polyglycidol is used as macroinitiator, densely grafted poly(glycidol-graft-epsilon-caprolactone) and poly(glycidol-graft-L-lactide) and loosely grafted poly[(glycidol-graft-epsilon-caprolactone)-co-glycidol] copolymers have been synthesized by chemical or, in the latter case, by enzymatic catalyzed ring-opening polymerization of epsilon-caprolactone and L-lactide. The well-defined copolymers possess similar molecular weights, but differ in their architecture, microstructure and chemical composition. The hydrolytic degradation behavior was studied in a phosphate buffer solution at pH 7.4 and 37 degrees C for up to 90 days. After different time periods, the mass loss was determined and the degraded copolymers were analyzed by means of NMR, size exclusion chromatography, and scanning electron microscopy. Compared to linear poly(epsilon-caprolactone), poly[(glycidol-graft-epsilon-caprolactone)-co-glycidol] shows a change of the degradation mechanism and a tremendous enhancement of polymer degradation. As this effect is attributed to the high concentration of hydroxy groups at the polyglycidol backbone, this work points out a new possibility to tailor the degradation profiles of polyesters by the introduction of functionality into the polymeric material.