A novel route to styrene/p-aminostyrene copolymers is described that involves the introduction of amino functionality into the structure of pure monodisperse polystyrene. The simple two-step synthesis involves the introduction of a bromo group into the aromatic ring by electrophilic substitution and then a palladium-catalyzed reaction with LiN(SiMe3)(2) followed by an acid and base treatment to release the free amine. All reactions are carried out at room temperature. This approach avoids the difficulties often associated with the preparation of copolymers from incompatible monomers. The technique also gives a product with a precisely known molecular weight and polydispersity, important parameters governing many physical properties. (c) 2007 Wiley Periodicals, Inc.