The nanostructures based on polymers have attracted much research interest because of their rich morphologies, unique properties and potential applications in various fields. In particular, helical nanostructures have been research hotspots in recent years. In this work, composite non-helical and helical nanowire arrays of atactic poly(2-vinylpyridine) (P2VP), and block copolymers polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) were fabricated successfully with inorganic species such as HAuCl4 through a liquid/liquid interfacial adsorption and self-assembly approach without addition of any chiral inducers. The formation process of the helical nanowires of P2VP includes the following steps, i.e. adsorption of the polymer molecules and HAuCl4 at the interface, the following protonation of pyridine groups, straightening of the P2VP chains by mutual repulsion between the protonated pyridine groups, aggregation of the P2VP chains due to the hydrophobic interactions between the backbones, and ordered organization of the pyridine groups through π-π interactions. The helical nanowires of PS-b-P2VP are worm-like micelles with a PS core and a P2VP shell, which are formed through the self-assembly of the block copolymer molecules with HAuCl4 within the interfacial phase with the help of hydrophobic interaction between the PS blocks and orderly stacking of the P2VP blocks. The different formation mechanisms reflected the effects of molecular structure on the self-assembly of polymers. In addition, the formed nanowires further self-organize into ordered arrays due to the increasing interfacial pressure during the generation of the nanowires. The results of this study expand the scope of research on polymer self-assembly and the application of liquid/liquid interfacial self-assembly techniques to acquire highly ordered supramolecular nanostructures. Display omitted •PS and PS-b-P2VP self-assembled into helical nanowires with chloroauric acid.•The nanowires formed in the liquid/liquid interfacial phase.•These nanowires further organized into parallel arrays.•The PS nanowires result from chain straightening, aggregation and ordered packing.•The PS-b-P2VP nanowires are actually worm-like micelles.