AbstractAiming to reduce the toxicity and operational costs often associated to chemical processes, the enzymatic synthesis is applied herein as a sustainable route for producing polyesters. The use of NADES’ (Natural Deep Eutectic Solvents) components as a source of monomers for the synthesis of polymers through lipase‐catalyzed esterification in an anhydrous medium is detailed for the first time. Three NADES composed by glycerol and an organic base, or acid, were used to produce polyesters, through polymerization reactions catalyzed by Aspergillus oryzae lipase. High polyester conversion rates (above 70 %), containing at least 20 monomeric units (glycerol:organic acid/base (1 : 1)), were observed by matrix‐assisted laser desorption/ionization‐time‐of‐flight (MALDI‐TOF) analysis. The NADES monomers′ capacity for polymerization, along with their non‐toxicity, cheap cost, and simplicity of production, sets up these solvents as a greener and cleaner approach for the synthesis of high value‐added products.