Hyperbranched poly(ester)s from the renewable, abundantly-available, biomonomers, glycerol and adipic acid, may be prepared under conditions that permit control of molecular weight, avoid gelation, and ensure the presence of hydroxyl endgroups. Capping the endgroups as esters provides materials that are thermally stable, fluid at room temperature, fully compatible with a PVC matrix and provide effective plasticization of PVC at low levels of incorporation. Because of low toxicity and migratory potential, these materials represent attractive alternatives to traditional toxic plasticizers for PVC.