Following up on previous preliminary communications the synthesis of a series of block copolymers by applying amine end-capped polymers as initiators for the nickel(II) catalyzed polymerization of isocyanides is reported. Using a polystyrene derivative as the initiator, superamphiphiles containing a hydrophobic polystyrene tail and a charged helical polyisocyanide headgroup were prepared. Under proper conditions these superamphiphiles self-assembled in water to give a variety of aggregate morphologies, among which are superhelical architectures. Initiators derived from carbosilane dendritic wedges gave block copolymers with a unique combination of structural elements, i.e. a flexible dendritic block and a rigid polyisocyanide block. Block copolymers derived from the 3rd generation dendrimers form welldefined micellar aggregates in the presence of Ag+ ions. These aggregates have been used to construct nanoarrays of metallic silver. (C) 2004 Elsevier Ltd. All rights reserved.