Highly ordered hybrid metallic–polymeric assemblies were prepared by simultaneously combining two organization-directing tools: the liquid crystalline behavior of high aspect ratio silver nanowires (Ag-NWs) dispersed in poly(vinyl alcohol) (PVA) aqueous solutions and a cryogenic technique based on the directional freezing of the liquid crystal-like systems. This combination allowed us to render highly oriented Ag-NWs inside macroporous PVA scaffolds. As a consequence of the compact self-assembly of NWs into the structured composites, electrically conductive metallic–polymeric hybrid materials were obtained.