An acrylated hyperbranched poly(ester-amine) (HPEA) synthesized from piperazine and trimethylolpropanettiacrylate at a molar ratio of 1:1.42 was used as the polycation to form self-assembled films by layer-by-layer dipping with poly(sodium-p-styrenesulfonate) as the polyanion. The surface morphology and hydrophilicity of the films with HPEA as the outmost layer were controlled by adjusting the solution pH of HPEA. Due to the existence of many acrylate groups, the films with HPEA as the outmost layer were further reacted with a series of reagents, including piperazine, piperidine, laurylamine and p-phenylenediamine. The surface reactions of the films depended on both the nature of the reagents and the morphology of the initial surface. In the presence of the strong basic amines, piperazine and piperidine, the films dissolved extensively into the solution. In the case of laurylamine, a modified film with an opaque appearance was obtained due to the crystallization of long alkyl chains. With the weak basic amine p-phenylenediamine as the reactant, the film was effectively modified without any change in the surface morphology. (c) 2006 Elsevier B.V. All rights reserved.