In this research, hydroxyl-terminated polyether-block-polydimethylsiloxane (PESO) was synthesized as an intermediate through the hydrosilylation of Si-H-terminated polydimethylsiloxane with allyl polyoxyethylene polyoxypropylene ether. Then, carboxylated polyether-block-polydimethylsiloxane (CPES) was prepared through the reaction of maleic anhydride with PESO. First, the chemical structures of the synthesized polysiloxanes were characterized with IR and H-1-NMR spectroscopy, and then the film morphology of CPES and the supermolecule self-assembled from CPES and N-beta-amino-ethyl-gamma-aminopropyl polydimethylsiloxane (ASO-1) was investigated by atomic force microscopy in detail. Experimental results indicated that the superpolysiloxane that self-assembled from CPES and ASO-1 showed a film morphology very different from those of CPES and ASO-1. There were not only many small, bright dots but also some big and marvelous dots circled by dots on the film surface. The morphology of dots circled by dots was estimated to result from aggregates of CPES micelles adsorbed onto the curled ASO-1 molecule interface. (C) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 110: 2595-2600, 2008