A modular approach toward the synthesis of polymers containing dendron groups as side chains is developed using the Diels-Alder "click" reaction. For this purpose, a styrene-based polymer appended with anthracene groups as reactive side chains was synthesized. First through third-generation polyester dendrons containing furan-protected maleimide groups at their focal point were synthesized. Facile, reagent-free, thermal Diels-Alder cycloaddition between the anthracene-containing polymer and latent-reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers. The efficiency of this functionalization step was monitored using H-1 and C-13 NMR spectroscopy and FTIR and UV-vis spectrometry. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 410-416, 2010