This article describes a divergent strategy to prepare dendrimer-like macromolecules from vinyl monomers through a combination of atom transfer radical polymerization (ATRP) and click reaction. Firstly, star-shaped polystyrene (PS) with three arms was prepared through ATRP of styrene starting from a three-arm initiator. Next, the terminal bromides of the star-shaped PS were substituted with azido groups. Afterwards, the azido-terminated star-shaped PS was reacted with propargyl 2,2-bis((2'-bromo-2'-methylpropanoyloxy)methyl)propionate (PBMP) via click reaction. Starshaped PS with six terminal bromide groups was afforded and served as the initiator for the polymerization of styrene to afford the second-generation dendrimer-like PS. Iterative process of the aforementioned sequence of reactions could allow the preparation of the third-generation dendrimer-like PS. When the second-generation dendrimer-like PS with 12 bromide groups used as an initiator for the polymerization of tert-butyl acrylate, the third-generation dendrimer-like block copolymer with a PS core and a poly (tert-butyl acrylate) (PtBA) corona was afforded. Subsequently PtBA segments were selectively hydrolyzed with hydrochloric acid, resulting an amphiphilic branched copolymer with inner dendritic PS and outer linear poly(acrylic acid) (PAA). Following the same polymerization procedures, the dendrimer-like PS and PS-block-PtBA copolymers of second generation originating from six-arm initiator were also synthesized. (C) 2007 Wiley Periodicals, Inc.