Aliphatic polyesters such as polylactides (PLAs) and other polylactones are thermoplastic, biodegradable and biocompatible polymers with the potential to replace petro-chemical-based synthetic polymers. A benign route for synthesizing these polyesters is through the enzyme-catalyzed ring-opening polymerization (ROP) reaction; this type of enzymatic process is very sensitive to reaction conditions such as solvents, water content and temperature. This review systematically evaluates the crucial roles of different solvents (such as solvent-free/in bulk, organic solvents, supercritical fluids, ionic liquids, and aqueous biphasic systems) on the degree of polymerization and polydispersity. In general, many studies suggest that hydrophobic organic solvents with minimum water contents lead to efficient enzymatic polymerization and subsequently high molecular weights of polyesters; the selection of solvents is also limited by the reaction temperature, e.g. the ROP of lactide is often conducted at above 100 degrees C, therefore, the solvent typically needs to have its boiling point above this temperature. The use of supercritical fluids could be limited by its scaling-up potential, while ionic liquids have exhibited many advantages including their low-volatility, high thermal stability, controllable enzyme-compatibility, and a wide range of choices. However, the fundamental and mechanistic understanding of the specific roles of ionic liquids in enzymatic ROP reactions is still lacking. Furthermore, the lipase specificity towards l- and d-lactide is also surveyed, followed by the discussion of engineered lipases with improved enantioselectivity and thermal stability. In addition, the preparation of polyester-derived materials such as polyester-grafted cellulose by the enzymatic ROP method is briefly reviewed. (c) 2017 Society of Chemical Industry