Supramolecular A(2)B rod-coil copolymer, composed of two polystyrene (PSt) arms and one oligo(para-phenyleneethynylene) (OPE) arm linked via ionic bond, has been designed and successfully synthesized. First, a trifunctional initiator, methyl 1, 3-bis(bromomethyl)benzonate, was prepared and used to initiate the polymerization of styrene under atom transfer radical polymerization (ATRP) condition to provide polystyrene (PSt) carrying monoester group at the middle of polymer chain. Then, the ester group was transferred into tertiary amino group to give amino-functionalized PSt, (PSt)(2)-N(CH3)(2), Subsequently, the ion-bonded rod-coil copolymer, (PSt)(2)-OPE, was obtained by the reaction Of (PSt)(2)-N(CH3)(2) with carboxy-terminated OPE (OPE-COOH). The resulting copolymer was characterized by nuclear magnetic resonance (NMR), Fourier transformer infrared (FTIR), and gel permeation chromatography (GPC) techniques. Vesicles and spherical micelles were generated from this supramolecular rod-coil copolymer through the manipulation of the initial polymer concentration in toluene. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7667-7676, 2008