Simultaneous characterization of the degree of branching and molar mass on a molecular level for hyperbranched polymers is still strongly limited. Therefore model hyperbranched polyesters for development of new chromatographic techniques on the basis of 2,2-bis(hydroxymethyl)propionic acid were synthesized. The two types of OH-functionalities (linear and terminal) of the hyperbranched polymer were selectively modified using different protection groups. The modification of the terminal end groups was carried out using their diol character with the formation of a ketal ring without changing the chemical structure of the linear OH groups. In order to obtain completely non-polar polymer, the linear OH-units were functionalized with an acetyl group. The last modification step was the deprotection of the terminal end groups by removing the ketal ring. Fractions with various molar masses for each modification stage were obtained by preparative fractionation. Extensive characterization by SEC-MALLS, NMR spectroscopy, and viscosity measurements elucidated the dependence of the molecular shape in solution on the polarity. These results were supported by molecular dynamic simulations. (C) 2010 Elsevier Ltd. All rights reserved.