Dendron-like branched polystyrenes are prepared using atom transfer radical polymerization (ATRP) and chain-end functionalization. The growing chain ends of polystyrene from ATRP are end-capped with 1,4-benzoquinone to incorporate branching points and ATRP initiating groups to the chain ends. Sequential ATRP of styrene initiated from the chain ends builds up the polystyrene arms. The number-averaged molecular weights of the first, second, and third generations of dendron-like polystyrene polymers calculated from their respective (1)H NMR spectra are 5960, 6850, and 9150 g/mol, respectively. The NMR-data are consistent with the molecular weights determined by GPC. An approach to prepare dendron-like polymers through ATRP and chain-end functionalization is developed. (C) 2009 Elsevier Ltd. All rights reserved.