A series of well-defined methacrylate-functionalized polyester dendrimers based on 2,2-bis(methylol)propionic acid (bis-MPA) has been synthesized divergently. The thermal properties and conversion of the methacrylate functional dendrimers are investigated along with the structure-property relationship of networks composed of the methacrylate dendrimers and two commercially available trifunctional thiols, trimethylolpropane tri(3-mercaptopropanoate) (TRIS) and ethoxylated trimethylolpropane tri(3-mercaptopropanoate) (ETTMP). The thiol-methacrylate reactions were conducted at room temperature, under ambient conditions, and triggered by UV light in the presence of a photoinitiator. Crosslinked films were obtained and characterized with respect to conversion (FT-Raman) and thermal (DSC and TGA) properties. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5815-5826, 2009