High-molecular-weight polymers with defined architectures are generally prepared by atom transfer radical polymerization. In order to prepare biodegradable structures different polymerization techniques have to he used. Here we present the successful synthesis of biodegradable starlike poly(glycidol-graft-6-caprolactone) copolymers by a combination of anionic and coordinative ring-opening polymerization, their characterization by static and dynamic light scattering and their visualization by scanning force microscopy.