We report the synthesis of two 2nd generation dendritic terpolymers consisting of poly(butadiene) (PB) of 1,4 geometric isomerism, poly(isoprene) (PI) enriched in 314 geometric isomerism (at least 55% PI3,4) and polystyrene (PS). The main focus of this work was the synthesis of well-defined dendritic terpolymers exhibiting high levels of molecular and compositional homogeneity. The preparation of these materials was achieved via anionic polymerization techniques in combination with chlorosilane linking chemistry. The molecular characterization of the intermediate products and the final dendritic materials was accomplished via gel permeation chromatography, membrane osmometry, differential scanning calorimetry, and H-1-nuclear magnetic resonance spectroscopy, leading to the conclusion that they can be considered model polymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1567-1574, 2009