A family of nonphthalate plasticizers derived from well-defined glycerol/adipic acid hyperbranched poly(ester)s has been prepared. Glycerol and adipic acid are both renewable biomaterials of low toxicity. Polymerization may be accomplished under conditions that allow control of molecular weight, avoid gelation, and ensure the presence of hydroxyl end groups. Capping the end groups as esters affords materials that are effective plasticizers for PVC. These materials are thermally stable, are fully compatible with a PVC matrix, provide effective plasticization at acceptable levels, display low migratory potential, and do not accelerate degradative dehydrochlorination.