A range of block copolymers (BCs) consisting of a linear poly(methyl methacrylate) (PMMA) block linked to an aliphatic polyester dendron functionalized with azobenzene moieties have been synthesized by sequential atom transfer radical polymerization (ATRP) and Click Chemistry. Two alkyne-functionalized PMMA homopolymers with different molecular weights were obtained by ATRP and coupled to generations 2 to 4 of azodendrons bearing an azide group at the focal points. In the case of the azodendron with the highest generation number, the length of the flexible spacer attaching the cyanoazobenzene units to the dendron has also been modified. The coupling of both blocks and purity of BCs were checked by gel permeation chromatography, nuclear magnetic resonance, and infrared spectroscopy. The thermal transitions and liquid crystalline behavior of the BCs were investigated by differential scanning calorimetry and polarized-light optical microscopy. A morphological study was carried out by transmission electron microscopy, using samples annealed at 115 degrees C. Photo-induced anisotropy was induced in thin films of these materials after annealed at 115 degrees C. The highest stable birefringence values were obtained for the BCs bearing 8 and 16 azobenzene units in the dendritic block. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48:1538-1550,2010