Ionic liquid-based 2D ion-conductive liquid crystals were obtained by the co-assembly of imidazolium salts and cationic calamitic liquid crystals with an imidazolium moiety at the end of the molecule through a flexible spacer. They exhibit smectic A phases. The two components are compatible over a wide range of compositions for ionic liquids with various anions. This organization of ionic liquids enhances the ionic conductivities of calamitic ionic liquid crystals. These liquid-crystalline mixtures dissolve lithium salts. The 2D ion-conductive pathways formed by the ionic liquid crystals and ionic liquids act as ion-conductive media for lithium ions.