The enantioselective polymerization of methyl- substituted is an element of-caprolactones using Novozym 435 as the catalyst was investigated. All substituted monomers could be polymerized except 6-methyl-is an element of-caprolactone (6-MeCL), which failed to propagate after ring opening. Interestingly, an odd-even effect in the enantiopreference of differently substituted monomers was observed. The combination of 4-methyl-is an element of-caprolactone with Novozym 435 showed good enantioselectivity also in bulk polymerization and resulted in enantiomerically enriched P((S)-4-NleCL) (ee(p) up to 0.88). Subsequently, a novel initiator combining a primary alcohol to initiate the ring opening polymerization and a tertiary bromide to initiate atom transfer controlled radical polymerization (ATRP) was synthesized, and showed high initiator efficiencies (> 90%) in the ring opening polymerization of 4-methyl-is an element of-caprolactone in bulk. In addition, the enantioselectivity was retained (E = 11). By using Ni(PPh3)(2)Br-2 as the ATRP catalyst, Novozym 435 could be effectively inhibited at the desired conversion of 4-methyl-is an element of-caprolactone, thus ensuring a high enantiomeric excess in the polymer backbone. At the same time, Ni(PPh3)(2)Br-2 catalyzed the ATRP of methyl methacrylate resulting in the formation of P((S)-4-MeCL-b-MMA) block copolymers. By this combination of two inherently different polymerization reactions, chiral P((S)-4-MeCL-b-MMA) block copolymers can be conveniently obtained in one pot without intermediate workup.