The development of novel supramolecular materials with nanometer-scale architectures and the effect of these architectures on the materials' properties are currently of great interest in molecular design. Liquid crystalline assemblies of rod-like mesogenic molecules containing flexible coils (rod-coil molecules) provide a facile entry into this area. Rod-coil molecules have been demonstrated to self-assemble into a rich variety of different liquid crystalline structures of nanoscale dimensions through the combination of shape complementarity and repulsive interaction of rigid and flexible parts as an organizing force. The mesophases include smectic, hexagonal or rectangular columnar, bicontinuous cubic, hexagonal channeled lamellar, barrel-like, honeycomb-like, and discrete micellar phases. The unconventional mesophases are induced by changing the rod-to-coil volume fraction, controlling the number of rod-coil repeating units, designing novel shapes of rod-coil molecules, and increasing the rod-coil molecular length.