Aliphatic polyesters have many applications in the biomedical field due to their properties and facile degradation. They are commonly synthesized via ring opening polymerization (ROP) with metal-based catalysts, but as high temperatures are needed and the products contain metal, organocatalysts are now widely adopted to polymerize them at room temperature while also ensuring short reaction times. Here, 1,7,7-triazabicyclo[4.4.0]-dec-5-ene is used to polymerize less reactive but renewably-derived lactones, namely delta-decalactone and delta-dodecalactone. These monomers were chosen in the attempt of creating renewable and highly lipophilic materials for drug delivery applications as alternatives to the more traditional, but non-renewable-valerolactone and -caprolactone. A combination of ROP and living radical polymerization Reversible Addition-Fragmentation Chain Transfer is proposed here to synthesize grafted block copolymers. They are able to self-assemble in water, forming micelles where the lipophilic polyester core is able to entrap a lipophilic drug, thus making the system a good candidate for drug delivery. (C) 2017 Wiley Periodicals, Inc.