An effective route was demonstrated to fabricate vesicles, cylindrical micelles, fibers and hierarchical structures by using dendritic-linear amphiphilic diblock complex as building block through hydrogen bonding. We tailored the formation and evolution of these aggregation morphologies as well as the transformation among them, and found that the concentration and solvent polarity could affect the aggregation states of the complex in solution and the self-assembling process on solid substrate. Additionally, the flexible-rigid structure of the complex and the template effect of DMSO droplets resulting from solvent evaporation also play important roles in constructing higher level organized structures such as hierarchical wreath-like and hollow entanglement self-assemblies at solid-gas interface. The cast film of the complex which possesses a fibrous structure shows superhydrophobicity and when the solution was allowed to stand for some days, a transparent organic gel spontaneously formed from the mixed solution. Based on the experiment results, the hierarchical architectures are proposed to derive from primary fibrils. The structure of the cylindrical micelle is believed to possess an alkyl chain block shell and a poly(ethylene oxide) block core, which is consistent with the water contact angle measurement and the simulation to the volume ratio of the two blocks of the complex. (C) 2007 Elsevier Ltd. All rights reserved.