The combination of inexpensive Fe(ii) acetate with low molecular weight aliphatic carboxamidesin situgenerates an effective catalyst system for the ring opening polymerisation of lactones. PLLAs were produced in melt conditions with molar masses of up to 15 kg mol−1, narrow dispersity (Đ= 1.03), and without racemisation. The catalytic system was investigated in detail with regard to Fe(ii) source, and steric and electronic effects of the amide's substituents. Furthermore, the synthesis of PLLA-PCL block copolymers of very low randomness was achieved. This commercially available, inexpensive, modular, and user-friendly catalyst mixture may be suitable for polymers with biomedical applications.