The chemoenzymatic cascade synthesis of block copolymers combining enzymatic ring opening polymerization (eROP) and atom transfer radical polymerization (ATRP) is reviewed. Factors like reaction condition and initiator structure were investigated and optimized prior to the polymerization. The synthesis of block copolymers was successful in two consecutive steps, i.e. eROP followed by ATRP as evident from SEC and GPEC analysis. While in the one-pot approach, block copolymers could be obtained by sequential addition of the ATRP catalyst, side reactions were observed when all components were present from the start of the reaction. A successful one-pot synthesis was achieved by conducting the reaction in supercritical carbon dioxide. 216