This review presents an updated and alternative perspective on enzymatic synthesis to obtain polyesters, with a focus on the precursor materials for absorbable sutures: poly‐lactic, poly‐glycolic, and poly‐lactic‐co‐glycolic acids. Currently, the profitable path towards the industrial synthesis of polyesters is ring‐opening polymerization (ROP) of lactones, which is an experimentally complex process and implies a hazardous environmental impact due to the need for energy consumption, use of large volumes of toxic organic solvents and of non‐biocompatible metal‐based catalysts. On the contrary, enzymatically driven reactions may be performed under mild conditions in simple reactors. Mechanistic and experimental issues of the two major biocatalyzed strategies ‐direct condensation and ROP‐ were analyzed from a green chemistry perspective. These enzyme‐catalyzed poly‐esterifications often return low yield and/or low final molecular weight (Mw). Considering all the analyzed published data available, possible strategies to overcome these limitations were postulated: implementation of aqueous biphasic reaction systems, use of ultrasound agitation and sequential addition of reactants or co‐solvents. To promote Mw increment, post‐reaction treatments can be carried out such as thermally induced short‐chain polymerization under vacuum and incorporation of glycols as chain extenders.