Self-assembly of liquid-crystalline molecules that combine order and fluidity is one of promising approaches to the preparation of nanostructured functional materials. Here we present a development of liquid-crystalline materials exhibiting anisotropic ionic conductivities by self-organization of ionic liquids. A new class of liquid-crystalline materials with layered (smectic) and cylindrical (columnar) structures was prepared by supramolecular association of conventional ionic liquids and hydrogen-bonded mesogenic molecules and by the chemical modification of ionic liquids. These materials formed nano-segregated structures consisting of ion-conducting and insulating parts in the liquid-crystalline states. Anisotropic ionic conductivities were induced by the formation of a single domain in the liquid-crystalline phases and the macroscopic alignment of the ion-conductive paths. Free-standing ion-conductive polymer films were also prepared by fixation of aligned structures of polymerizable liquid-crystalline ionic liquids through photoirradiation.