Polyesters are currently synthesized by a step-growth mechanism from a mixture of a diol and a diacid (or a diacid derivative), or from a hydroxy-acid when available. Ring-opening polymerization (ROP) of lactones and related compounds is an alternative method for the synthesis of aliphatic polyesters. Comparison of these two mechanisms is clearly in favor of the polyaddition process. The drawbacks of polycondensation are well known:high temperatures and long reaction times are required to produce high-molecular-weight chains. Even though conversion of the hydroxyl and acid group is close to completion, any departure from the reaction stoichiometry has a very detrimental effect on the chain length.